CN1747782A - Process for manufacturing ethylene oxide - Google Patents
Process for manufacturing ethylene oxide Download PDFInfo
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- CN1747782A CN1747782A CN200380109763.XA CN200380109763A CN1747782A CN 1747782 A CN1747782 A CN 1747782A CN 200380109763 A CN200380109763 A CN 200380109763A CN 1747782 A CN1747782 A CN 1747782A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/06—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by affecting the pattern of flow of the heat-exchange media
- F28F13/08—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by affecting the pattern of flow of the heat-exchange media by varying the cross-section of the flow channels
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
- B01J2208/00212—Plates; Jackets; Cylinders
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- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The present invention relates to a process for manufacturing ethylene oxide by the catalytic oxidation reaction of ethylene by molecular oxygen in a tube reactor. The reactor comprises a bundle of reaction tubes (5) which are immersed in a heat exchange fluid and filled with a solid silver-based catalyst (8) and which are traversed by a reactive gas current containing ethylene and molecular oxygen, which in contact with the catalyst forms the ethylene oxide. The area of the internal cross-section of the reaction tubes (5) decreases between the inlet (1) and the outlet (3) of the tubes over at least a portion of the length of the tubes and remains constant over any remaining portion. The process makes it possible to increase the selectivity of the reaction to ethylene oxide for a given production of ethylene oxide. It also makes it possible to use a maximum charge of active catalyst per unit of internal tube volume available in the reactor, owing in particular to an optimum heat exchange capable more particularly of supplying a relatively stable reaction temperature profile over the whole length of the reaction tubes and preventing in particular reaction runaways.
Description
The present invention relates to a kind of method of utilizing the catalytic oxidation production oxirane of ethene.
It is strong exothermic reaction that the known catalytic oxidation that utilizes molecular oxygen and ethene forms oxirane.This type of reaction is carried out in tubular reactor usually, particularly carries out in vertical multiple row shell-and-tube heat exchanger type reactor or vertical tube shell heat exchanger type reactor.In general, tubular reactor comprises three continuous and adjoin cavitys, the reactive gas current that contains ethene and molecular oxygen is crossed described cavity: a reactive gas current entrance cavity is a center cavity (deriving from this cavity in the air-flow of catalytic oxidation and forming oxirane) and a product gas flow outlet plenum subsequently.Center cavity comprises a branch of reaction tube usually, and described reaction tube is dipped in the heat exchange fluid and is filled with solid silver-based catalyst.Reactive gas current enters reaction tube inside, causes generating oxirane in the air-flow that reaction produces by contacting with catalyst.Each reaction tube comprises an inlet and an outlet of stretching into outlet plenum of stretching into entrance cavity.In each reaction tube, there are three continuous zones exporting (promptly in the air current flow direction) from entering the mouth to usually, promptly be positioned at the preheating zone of described tube inlet, be reaction zone and the quenching or the cooling zone that are positioned at described pipe outlet then.
The desired product of ethylene catalytic oxidation reaction is an oxirane.Yet non-required side reaction may take place, and for example ethene and oxirane complete oxidation are carbon dioxide and water, and the oxirane isomery turns to acetaldehyde and ethene oxidation side reaction is converted into formaldehyde.Described side reaction reduces owing to the selectivity that ethylene catalytic oxidation generates reacting ethylene oxide.
Several problems have appearred in ethylene oxide production simultaneously.The most serious problem is to generate the strong exothermal nature of reacting ethylene oxide and the total length of the control of reaction temperature, particularly reaction tube (entering into the tubular reactor inlet again to the generated reactive gas mixture outlet from reaction gas mixture) about ethylene catalytic oxidation.A principal risk of described method is to form the heat spot (being commonly referred to " after-burning ") that causes runaway reaction and form carbon dioxide, carbon monoxide and aldehyde (for example formaldehyde and acetaldehyde), and some described side reaction product is difficult to separate from oxirane subsequently especially.Irregular reaction temperature profile, poorly controlled and particularly increase progressively and may not only cause producing heat spot along the reaction tube total length, also cause too high final temperature.Heat spot and too high end reaction temperature effect generate the selectivity of the reaction of oxirane.In addition, localized hyperthermia and too high final temperature can reach corresponding to the value of the maximum combustion temperature of this admixture of gas and therefore cause blasting.
Some partly solve some described problem by the method for differing complexity solution has been proposed.A kind of method of producing oxirane has been proposed among the Australian Patent AU 211 242, described method is to carry out in a tubular reactor, and this tubular reactor is formed by comprising an inlet region and a popular response pipe of vacating oral region that is filled with inert particle (as the aluminium oxide spheroid).Between described two zones, reaction tube comprises a reaction zone that is filled with money base carried catalyst (concentration increases progressively to outlet along the inlet in described zone).Consequently catalytic activity increases progressively along reaction tube to outlet from tube inlet at the reactive gas current flow direction.
U.S. Pat 5,292, proposed a kind of method of producing oxirane in 904, described method is to carry out in a tubular reactor, and this tubular reactor is formed by comprising a preheating zone and a popular response pipe that is positioned at the cooling zone of pipe outlet that is positioned at tube inlet.Described two districts are filled with inertia refractory product (for example fire-resistant aluminium oxide).
A kind of catalytic reaction method has been proposed in the International Patent Application WO 02/26370, described method is to carry out in a tubular reactor, and this tubular reactor is formed by comprising the upstream portion laying respectively at tube inlet and outlet and/or the popular response pipe of a downstream part.Described part comprises one mainly with the heat exchange plug-in unit of bar form, and this insert length equals 1 to 20% of reaction tube total length.When this method is used to produce oxirane, regulation reaction tube upstream and downstream partly comprises plug-in unit, and the insert length that is contained in upstream portion can be 1 to 10% of reaction tube total length, and the insert length that is contained in the downstream part can be the twice of insert length that upstream portion comprises.Yet it should be noted that in all situations, catalyst only occupies the core of reaction tube, and the overwhelming majority of reaction tube is filled with inert solid material and only be in order to promote heat exchange.Therefore sizable part of popular response pipe is not to be used to produce oxirane, has consequently influenced the output of the oxirane that available interior tube body amasss in the per unit reactor.
International Patent Application WO 03/01149 has been described a kind of tubular reactor that is used for the chemical conversion of organic compound exothermicity.Described tubular reactor comprises the reaction tube that is filled with catalyst, and reactive gas current is passed described reaction tube.Each reaction tube comprises one group of continuum, and each catchment has than the smaller or preferably larger cross section of upstream that links to each other.Yet as shown in the figure, the cross section of the reaction tube only current upstream from tubular reactor increases progressively, and described tubular reactor is used in particular for producing maleic anhydride and also is used to produce other organic compounds (for example phthalic anhydride, oxirane, acrylic acid, vinylacetate or ethylene dichloride).
German patent application DE 29 29 300 has described a kind of catalytic reactor that is used to move heat absorption or exothermic reaction, reacting fluid this reactor of flowing through, described reactor comprises and is filled with the reaction tube that carries out the catalyst material of thermo-contact with heat release or heat recipient fluid, the cross-sectional area that it is characterized in that reaction tube changes along the reacting fluid flow direction, changes size and depends on and finish the heat that is discharged in required heat of given reaction or the course of reaction.Yet as shown in figs. 1 and 4, the cross-sectional area of reaction tube reduces earlier to increase along the reacting fluid flow direction again, and cross-sectional area increases earlier and reduces among Fig. 2, and the cross-sectional area of some reaction tube increases and the cross-sectional area of other reaction tubes reduces in the reactor in Fig. 3, and cross-sectional area reduces in Fig. 5.Reactor described in the German patent application is proposed to be used in the synthetic of methyl alcohol or ammonia.Reactor shown in Figure 2 is exclusively used in synthesizing methanol (exothermic reaction).
The inventive method is used to solve above-mentioned technical barrier.Be used in particular for improving ethylene catalytic oxidation and generate the long-pending oxirane output of available interior tube body in the selectivity of reaction of oxirane and the per unit reactor, and by special control reaction temperature along the distribution situation of reaction tube total length and improve the security, particularly runaway reaction of method and the risk of blast simultaneously.
The present invention relates to a kind of method that is used for utilizing ethene and molecular oxygen to produce oxirane at the tubular reactor catalytic oxidation.Described tubular reactor comprises three continuous and adjoin cavitys, the reactive gas current that contains ethene and molecular oxygen is crossed described cavity, a reactive gas current entrance cavity, a center cavity (formation comprises the reaction product stream of oxirane) and a product gas flow outlet plenum.Center cavity comprises a branch of reaction tube, and described reaction tube is dipped in the heat exchange fluid and is filled with solid silver-based catalyst (reactive gas current is in contact with it and forms oxirane).Each reaction tube comprises an inlet and an outlet of stretching into outlet plenum of stretching into entrance cavity.The feature of described method is that the interior cross-sectional area of the regional reaction tubes of at least a portion tube length of reaction tube between the reaction tube entrance and exit reduces, and cross-sectional area keeps constant in remaining any zone is described.
Fig. 1 represents a tubular reactor that comprises reaction tube that is used for the inventive method.
Fig. 2 a, 2b, 3,4a and 4b represent the various reaction tubes that are used for the inventive method.
Fig. 5 represents that curve connects, and ordinate is reactive gas current temperature (measurement unit: degree centigrade), and abscissa be from the initial tube length of reaction tube of tube inlet (measurement unit: meter).This figure draws according to the condition of embodiment 1.
Fig. 6 represents that a curve connects, and ordinate is for generating the reaction selectivity (S) (representing with %) of oxirane, and abscissa is oxirane output (P) (representing with ton oxirane/sky).This figure be according to embodiment 1 and 2 and the condition of comparing embodiment 3 draw.
Find and to obtain metastable reaction temperature profile at the reaction tube overall length according to the present invention, to avoid runaway reaction and significantly to reduce the reaction final temperature, improve simultaneously the selective and output of the reaction of synthesize epoxyethane, cross-sectional area reduces on the reaction tube overall length from the reaction tube entrance to outlet (for example along the reactive gas current flow direction), perhaps reduces and especially true in all the other length maintenances constant condition lower times at least a portion length. Specifically, the shape of reaction tube so that the interior cross-sectional area of pipe can not increase in any part along the reaction tube of reactive gas current flow direction. Described area may reduce or preferred discontinuous reducing continuously, particularly reduces by level. In addition, all reaction tubes preferably have as previously mentioned according to interior cross section of the present invention in the tubular reactor.
When the interior cross-sectional area (A1) of reaction tube entrance than large 1.5 to 12 times of the interior cross-sectional area (A2) of described pipe outlet, preferred 2 to 10 times, most preferably 3 to 9 times the time, effect of the present invention is attractive especially.
In addition, described effect is especially remarkable under following condition.In the length of minimizing at pipe of cross-sectional area in the reaction tube, only take place once (to reduce continuously on a part of length at pipe, or discontinuous reducing, especially reduce by level) time, described minimizing may betide the back segment (along the reactive gas current flow direction) of pipe range, but in the end 1/5th sections (being positioned at outlet) before, before preferred last 1/4th sections, especially before preferred last 1/3rd sections, more preferably the pipe range second half section (being positioned at outlet) before, the perhaps leading portion of pipe range, but need after 1/3rd sections, (be positioned at inlet).When the minimizing of cross-sectional area in the reaction tube takes place double on pipe range or (no matter is that two or more partial continuous at pipe range reduce repeatedly, or discontinuous reducing, particularly on two or more continuous levels, reduce), described minimizing may betide the back segment (along the reactive gas current flow direction) of pipe range for the first time, but in the end 1/5th sections (being positioned at outlet) before, before preferred last 1/4th sections, before particularly last 1/3rd sections, more preferably the pipe range second half section (being positioned at outlet) before; The perhaps leading portion of pipe range, but need (be positioned at inlet) after 1/3rd sections is for example after preceding 5/12 section of pipe range (being positioned at inlet).
For example the length of reaction tube (L) can be 6 to 20m, and preferred 8 to 15m.Cross-sectional area (A1) is 12 to 80cm in the reaction tube inlet
2, preferred 16 to 63cm
2Cross-sectional area (A2) is less than (A1) and be 1.2 to 16cm in the reaction tube outlet
2, preferred 1.8 to 12cm
2
Described tubular reactor is generally vertical shell-tube heat exchanger type, that is to say to comprise a branch of vertical reaction tube.Bundle of reaction tubes typically refers to identical and parallel each other pipe assembly.According to a form of implementation of the present invention, reaction tube can be cylindrical and has cross section in the annular, and its internal diameter (Di) reduces at least a portion of the pipe range from tube inlet to outlet, and keeps constant at the remainder internal diameter.Therefore tube inner diameter (Di) can reduce on the full pipe range of the pipe range from tube inlet to outlet, and perhaps internal diameter reduces and keeps constant at the remainder internal diameter at least a portion pipe range.Internal diameter (Di) can reduce continuously along tube inlet to outlet or discontinuous reducing particularly reduces by level.Especially when reaction tube inlet internal diameter (D1i) bigger 1.2 to 3.5 times than described pipe outlet internal diameter (D2i), preferred 1.4 to 3.1 times, the more preferably result that can obtain 1.7 to 3 times the time.
Under following situation, also can obtain significant result.In the length of minimizing at pipe of tube inner diameter (Di), only take place once (to reduce continuously on a part of length at pipe, or discontinuous reducing, especially reduce by level) time, described internal diameter (Di) reduces and may betide the back segment (along the reactive gas current flow direction) of pipe range, but in the end 1/5th sections (being positioned at outlet) before, before preferred last 1/4th sections, especially before preferred last 1/3rd sections, more preferably the pipe range second half section (being positioned at outlet) before, the perhaps leading portion of pipe range, but need 1/3rd sections (being positioned at inlet) afterwards.When the minimizing of tube inner diameter (Di) is recurred on pipe range twice or repeatedly (two or more partial continuous at pipe range reduce, or discontinuous reducing, particularly reduce continuously) with two or more levels, described internal diameter (Di) reduces may betide the back segment (along the reactive gas current flow direction) of pipe range for the first time, but in the end 1/5th sections (being positioned at outlet) before, before preferred last 1/4th sections, before preferred last 1/3rd sections, more preferably the pipe range second half section (being positioned at outlet) before especially; The perhaps leading portion of pipe range, but need (be positioned at inlet) after 1/3rd sections is for example after preceding 5/12 section of pipe range (being positioned at inlet).
For example the length of cylindrical reaction tubes (L) can be 6 to 20m, and preferred 8 to 15m.Reduce between tube inlet and outlet according to internal diameter of the present invention (Di).Described internal diameter (Di) is chosen as 12 to 100mm, is preferably 15 to 90mm.In addition, reaction tube is chosen as 38 to 100mm at the internal diameter (D1i) of tube inlet, is preferably 45 to 90mm, and the internal diameter (D2i) of pipe outlet is less than D1i and be chosen as 12 to 45mm, is preferably 15 to 40mm.
According to the present invention, the interior cross-sectional area of reaction tube reduces between tube inlet and outlet.The pipe thickness of reaction tube can be constant or changes in addition, for example reduces or increases to exporting (reactive gas current flow direction) at tube inlet.Can use cylindrical reaction tubes especially, its internal diameter (Di) reduces that (for example the present invention is foregoing reduces or discontinuous reducing continuously between tube inlet and outlet, particularly reduce by level), its external diameter (De) keeps constant and equals the external diameter (D1e) of described tube inlet especially between tube inlet and outlet in addition.In this case, the reaction tube tube wall at tube inlet to the result who increases between the outlet not with significantly or only influence the effect of the inventive method in unessential mode.
The used solid silver-based catalyst of the present invention optional from can be under the assistance of molecular oxygen be the money base carried catalyst of oxirane with ethylene catalytic oxidation.This catalyst can be selected from the catalyst that mainly comprises the argent that is deposited on the fire-resistant solid carrier of porous.The refractory product of optional natural from deriving from, the artificial or synthetic of described carrier preferably has the material of macroporous structure, and more preferably specific area (B.E.T.) is less than 20m
2/ g (particularly 0.01 arrives 10m
2/ g) and apparent porosity greater than the product of 20% volume (particularly 30 to 70% volumes).Only carrier can be those carriers that comprise siliceous and/or the aluminium matter product product of silica and/or aluminium oxide (respectively based on).For example carrier can be selected from aluminum oxide (especially those are with trade mark " Alundum "
Well-known aluminum oxide), active carbon, float stone, magnesia, zirconium, diatomite, bleaching earth, carborundum, the porous agglomerate that comprises silicon and/or carborundum, clay, natural, artificial or synthetic zeolite, comprise the metal oxide gel sill and the ceramic product of heavy metal (as molybdenum or tungsten) oxide.Aluminium matter product preferred those especially comprises alpha-type aluminum oxide, and specific area (B.E.T.) is 0.15 to 0.6m
2/ g and apparent porosity are the product of 46 to 52% volumes.The B.E.T. method of measurement the specific area sees and is set forth in J.Am.Chem.Soc., 60, and 309-16 (1938).
Described catalyst can comprise 1 to 20%, the silver of preferred 2 to 16% weight.It can also comprise at least a metal promoters in addition, and described metal promoters is selected from alkali metal, alkaline-earth metal (as calcium or barium) and other metals (as thallium, antimony, tin or rhenium) especially.Described catalyst can particle form exist, the average diameter minimum equals 1 or half of 2mm and the maximum minimum diameter that equals the reaction tube that uses, especially average diameter is selected from 1.5 and arrives 15mm, preferred 4 arrive 8mm.It for example is the form of sphere or hemi-spherical granule, ring, ball or particulate.Described catalyst can prepare according to the whole bag of tricks, and for example U.S. Pat 3,043, and 854, US 3,207,700, US 3,575,888, US 3,702,259 and US3,725,307, the perhaps method of describing in the European patent EP 0 266 015.
An advantage of the invention is can use from tube inlet to outlet (especially being positioned at the zone of outlet) whole or at least almost all (that is to say more than 95%) pipe range include the reaction tube of catalyst.The device (for example grid or spring) that is used for the bearing catalyst material only occupies a part of pipe range of being positioned at outlet (general maximum equal pipe range 5%).Therefore owing to the special configuration of reaction tube of the present invention, available interior tube body amasss the catalyst feed that can load maximum in the reactor.Described material has activity to ethylene oxide production simultaneously.This is external to have obtained described favourable result when keeping the reaction high selectivity that generates oxirane and provide metastable Temperature Distribution especially on whole pipe ranges.Yet if desired, can in reaction tube, add inert solid material or preferably catalyst is mixed (if feasible) with described material.This inert solid material can be chosen wantonly and be selected from inert particle or solid and particularly hollow insert; for example metal or metal alloy perhaps are particularly useful as the inertia refractory product (for example being the form of powder, sphere or hemi-spherical granule, ring, ball or particulate) of solid, inert filling product.The optional inertia refractory product that uses can have identical or different character with carrier of the present invention.Their optional self-catalysis agent carriers, particularly carrier and have less B.E.T. specific area and (preferably less than 0.1, be more preferably less than 0.05, as previously mentioned especially preferably less than 0.01m
2/ g) refractory product.Refractory product with less B.E.T. specific area can be selected from silica, aluminium oxide, carborundum, aluminium oxide and silica mixture, and described mixture is optional by alkali metal or alkaline-earth metal, ceramic product, glass-type materials (as containing the sodium polysilicate that is in particular the stoichiometric amount excess silicon dioxide) modification.
The method of producing oxirane adopts molecular oxygen, and this molecular oxygen can purified molecule oxygen form (for example oxygen purity is equal to, or greater than 95% volume) use or use with air form.Crossing the reactive gas current of tubular reactor can and choose any one kind of them or multiple other gases and at least a halogenated hydrocarbons for example chloroethanes, the vinyl chloride or 1 of being selected from especially that is selected from carbon dioxide, nitrogen, argon gas, methane, ethane by ethene, molecular oxygen, and the reaction suppressor of 2-dichloroethanes or the admixture of gas of moderator are formed.In reactive gas current, the ethylene concentration height of will trying one's best usually more particularly is to be equal to or less than 40% volume, and is selected from 15 to 35% volumes especially.The concentration of molecular oxygen can be selected from 3 to 20% in the reactive gas current, preferably from 4 to 10% volumes.Concentration of carbon dioxide is generally less than or equal to 10% volume in the reactive gas current, and can be selected from 4 to 8% volumes.Methane and/or nitrogen can be used as diluent in reactive gas current, more particularly be to move into for the combustion limits that reduce admixture of gas and with it to use the zone.Therefore methane and/or the concentration of nitrogen in the reactive gas current height of can trying one's best.For example reactive gas current can comprise the ethene of 1 to 40% volume, the molecular oxygen of 3 to 12% volumes, the carbon dioxide of 0 to 10% volume, the ethane of 0 to 3% volume, the halogenated hydrocarbon type reaction suppressor or the moderator of 0.3 to 5,000 ten thousand parts by volume (vpm), and all the other are argon gas and/or nitrogen and/or methane.The absolute pressure of reactive gas current can be selected from 0.1 to 4MPa in the tubular reactor, and preferred 1 to 3MPa.The volume space-time speed (VSHV) of reactive gas current can be selected from 1000 to 10000h in the reaction tube
-1(m
3/ m
3.h catalyst), be preferably 2000 to 8000h
-1, described value is measured under the standard temperature and pressure (STP) condition.
Reactive gas current can advantageously be preheating to 100 to 200 ℃, preferred 140 to 190 ℃.The temperature of reactive gas current can be selected from 140 to 350 ℃ in the reaction tube, preferred 180 to 300 ℃, more especially is selected from 190 to 280 ℃.Adopt method of the present invention, the temperature of the reactive gas current of reaction tube inlet can be very rapidly or rise at once 210 ℃ or more than.Temperature can continue to raise and reach maximum temperature, but growth rate is more slow, described maximum temperature is the most high in 270 ℃, preferably the most high in 265 ℃, more especially the most high in 260 ℃, the zone of described variations in temperature is that the pipe range of reactive gas current direction extends from first part of 1/4th to 4/5ths, preferably long 3/4ths the part to pipe range of first semicanal.The self-reacting gas flow temperature in source of reaction tube outlet can keep described maximum temperature or preferably be reduced to being equal to or less than 250 ℃, preferably be equal to or less than 240 ℃, more especially be equal to or less than 230 ℃, for example 180 to 250 ℃, preferred 190 to 240 ℃ more especially is 200 to 230 ℃.
It should be noted that the method for the present invention that adopts especially, making along the heat exchange of reaction tube that this method can make up metastable reaction temperature profile and per unit reactor simultaneously can be with the following catalyst of the optimum activity state of pipe inner volume maximum (pipe total length and more especially manage the zone that exports being positioned at).Described combination makes this method can prevent that the suitable major part of reaction tube from wasting in other purposes, but not be used to generate oxirane and keep pipe inner catalyst material (more particularly quite most of pipe range does not contain catalyst), unique target is the control heat exchange and prevents heat spot.A major advantage of the inventive method also is to come from the temperature of the air-flow that reaction generates of reaction tube outlet and compares with conventional method and can reduce at least 5 ℃ significantly, and for example reduction is at least 10 ℃.The significantly reduced result of described temperature also is like this to other any the same terms in addition, for example the molecule keto concentration in the reactive gas current is identical, and the combustion limits of described air-flow are can the phase strain big and therefore allow safer method is provided and need not to sacrifice the productive rate and the selectivity of the reaction that generates oxirane in the middle of this.
Bundle of reaction tubes is immersed in the heat-exchange fluid, and described heat-exchange fluid can be selected from organic heat transport fluid and pressurization superheated water (being in the water of saturation temperature) especially.Described organic heat transport fluid can be the mixture of oils or hydro carbons (straight chain or the branched paraffin that have the boiling point that is higher than maximum reaction temperature especially).Can be 100 to 1500kPa, preferred 200 arrive 800kPa, and more especially 200 to 600kPa relative pressures use organic heat transport fluid down.Described organic heat transport fluid can be selected from Exxon " Isopar " , Monsanto " Therminol " and DowChemicals " Dowtherm " especially.Can be according to Fig. 1 or 2 in the European patent application EP 0 821 678, perhaps U.S. Pat 4,759, and 313 described methods and heat exchanger use described heat transport fluid.Heat-exchange fluid also can be pressurization (especially using under relative pressure 1500 to 8000kPa) superheated water.In this case, can be according to U.S. Pat 5,292,904 described methods and heat exchanger use described superheated water.The temperature of the heat-exchange fluid of tubular reactor outlet is generally 210 to 300 ℃, and preferred 220 to 280 ℃, more especially 210 to 280 ℃.The temperature of the heat-exchange fluid of tubular reactor inlet is generally 120 to 250 ℃, and preferred 130 to 240 ℃, more especially 130 to 230 ℃.
Method of the present invention can advantageously be implemented in a continuous manner, more especially by utilizing reactive gas current (this air-flow passes through three cavitys of tubular reactor successively and continuously) continuously and reclaiming the air-flow that comprises oxirane of reaction generation and advantageously enforcement continuously at reactor outlet.
Fig. 1 is the schematic diagram of tubular reactor that the inventive method is used.Described tubular reactor is vertical shell and tube heat exchanger type.This reactor comprises three continuous and adjoin cavitys: an entrance cavity (1), a center cavity (2) and an outlet plenum (3).Entrance cavity (1) is connected with a pipeline (4) and is used to import the reactive gas current that comprises ethene and molecular oxygen.Center cavity (2) comprises a branch of parallel to each other and identical reaction tube (5) (pref. cylindrical), and each pipe (5) comprises inlet (6) that is connected to entrance cavity (1) and the outlet (7) that is connected to outlet plenum (3).Reaction tube (5) is filled with solid silver-based catalyst (8) (representing with light gray) at its full pipe range or almost full pipe range (the device of bearing catalyst material, as grid or spring, Fig. 1 does not show in pipe).(9) are discontinuous reduces with three continuous levels between tube inlet (6) and outlet (7) for the interior cross-sectional area of each reaction tube (5), so each reaction tube (5) by four continuously and the tubular area (10) that adjoins forms, each zone at inlet (6) and export have between (7) ever-reduced in cross-sectional area.Reaction tube (5) is immersed in heat-exchange fluid (11), and described fluid imports center cavity (2) and derives center cavity (2) by drain tube (13) by conduit (12).Outlet plenum (3) is equipped with the conduit (14) that is used to derive the reaction product stream that comprises oxirane.
Fig. 2 a and Fig. 2 b are the schematic diagram of reaction tube (5), and described reaction tube (5) can be used in tubular reactor shown in the figure (1) and is used to carry out method of the present invention.The parts identical with parts shown in Figure 1 are indicated with identical coding among Fig. 2 a and the 2b.Fig. 2 a is the schematic diagram that is equipped with the reaction tube (5) of an inlet (6) and an outlet (7), and the interior cross-sectional area of described reaction tube (5) reduces between outlet (7) continuously at inlet (6).Fig. 2 b is the schematic diagram that is equipped with the reaction tube (5) of an inlet (6) and an outlet (7), the interior cross-sectional area of described reaction tube (5) reduces continuously in one section (15) of pipe range, and remaining tract (17) that is positioned at remaining Upstream section (16) of inlet (6) and is positioned at outlet (7) keeps constant.Reaction tube shown in Fig. 2 a and the 2b (5) is shown as blank pipe and loading catalyst (8) not as shown in Figure 1.
Figure 3 shows that according to the inventive method, can be used in the schematic diagram of the reaction tube (5) of tubular reactor shown in Figure 1.Parts identical with parts shown in Figure 1 among Fig. 3 are indicated with identical coding.Reaction tube (5) is equipped with an inlet (6) and an outlet (7).The interior cross-sectional area of described reaction tube (5) is discontinuous and reduce by two continuous grade (9) between (7) to outlet at inlet (6), so reaction tube (5) by three continuously and adjoin tubular area (10) and forms, each zone at inlet (6) and export have between (7) ever-reduced in cross-sectional area.Reaction tube shown in Figure 3 (5) is shown as blank pipe and loading catalyst (8) not as shown in Figure 1.
Fig. 4 a and Fig. 4 b are the schematic diagram of reaction tube (5), and described reaction tube (5) can be used in tubular reactor shown in the figure (1) and is used to carry out method of the present invention.The parts identical with parts shown in Figure 1 are indicated with identical coding among Fig. 4 a and the 4b.Fig. 4 a is the schematic diagram that is equipped with the cylindrical reaction tubes (5) of an inlet (6) and an outlet (7).In described reaction tube (5) circular cross-sectional area at inlet (6) to discontinuous between the outlet (7) and reduce by two continuous grade (9), so reaction tube (5) by three continuously and adjoin tubular area (10) and forms, each zone is at inlet (6) and export between (7) and have ever-reduced internal diameter (Di).The external diameter (De) of reaction tube (5) keeps constant between inlet (6) and outlet (7).Reaction tube (5) is in fact by three cylindrical and coaxial pipes (10
A, 10
BWith 10
C) successively the phase insert group become, therefore manage 10
BOuter surface with the pipe 10
AInner surface adjoin, the pipe 10
COuter surface with the pipe 10
BInner surface adjoin.Fig. 4 b is the schematic diagram that is equipped with the cylindrical reaction tubes (5) of an inlet (6) and an outlet (7).The internal diameter (Di) of described reaction tube (5) reduces continuously in one section (15) of pipe range, and keeps constant at remaining Upstream section (16) that is positioned at inlet (6) and remaining tract (17) of being positioned at outlet (7).The external diameter (De) of reaction tube (5) keeps constant between inlet (6) and outlet (7).Reaction tube (5) is in fact by two cylindrical and coaxial pipes (16
AWith 17
A) phase insert group one-tenth, so pipe (17 successively
A) outer surface and pipe (16
A) inner surface adjoin.Pipe (17
A) extend to and manage (15
A) adjoin pipe (15
A) and two pipes (16
AWith 17
A) coaxial.Pipe (15
A) have a cylindrical outer wall (surface with the pipe (16
A) inner surface adjoin) and one chamfer the circular cone inwall (with the pipe (17
A) diameter and the pipe (17 of the big bottom surface of adjoining
A) internal diameter identical; The diameter of its little bottom surface and pipe (16
A) internal diameter (Di) identical).Reaction tube shown in Fig. 4 a and the 4b (5) is shown as blank pipe and loading catalyst (8) not as shown in Figure 1.
The inventive method provides following advantage especially:
Significantly improve under the condition of-oxirane reaction of formation selectivity or par constant, for example at least 3 points (representing) with % at retaining ring oxidative ethane yield level;
The long-pending oxirane output of available interior tube body obviously improves in-per unit the tubular reactor;
The useful load of the active catalyst in the oxirane output that available interior tube body amasss in-per unit the tubular reactor reaches maximum;
-in the metastable reaction temperature profile of reaction tube total length;
-comparing the temperature that exports at reaction tube with conventional method significantly reduces;
-owing to service condition more makes the method for ethylene oxide production safer away from the combustion limits of air-flow;
-the amount of comparing the carbon dioxide that is generated with oxirane significantly reduces, and the amount of carbon dioxide that is discharged in the environment significantly reduces.
The selectivity (representing with %) that generates the reaction of oxirane can be calculated according to following formula:
(1) selectivity=100 * (oxirane mole output)/(ethene mole consumption)
The following example is used to illustrate the present invention.
In tubular reactor shown in Figure 1, carry out the production of oxirane continuously.Described tubular reactor comprises an entrance cavity (1), a center cavity (2) and an outlet plenum (3).Center cavity (2) comprises a branch of 3709 cylindrical reaction tubes (mutually the same and parallel).Each reaction tube (5) comprises two continuous levels (9) as shown in Figure 3, so pipe (5) is continuous by three and cylindrical tubular zone (10) that adjoin is formed, and each described zone length is that L and its internal diameter (Di) reduce between inlet (6) and outlet (7).The length (L) in continuous three zones (10) between tube inlet (6) and outlet (7) and the value of internal diameter (Di) are as follows: L=5m and Di=51.2mm; L=5m and Di=38.4mm; L=2m and Di=25.6mm.Fill argentum-based catalyzer in the reaction tube (5), the filling mode of each pipe is identical and all almost occupy full pipe range (96%) (spring that is used for the stay pipe inner catalyst only occupies the last 0.5m zone that is positioned at outlet (7)).Described catalyst is the silver catalyst on the aluminium oxide of being carried on that comprises 14.7% weight.The cumulative volume of the catalyst of the reaction tube of introducing reactor is about 62.5m
3
In tubular reactor, import 270.8 tons/hour of flows, absolute pressure 2.06MPa continuously, be preheating to about 150 ℃ reactive gas current, described reactive gas current comprises the ethene of 28.2% volume, the molecular oxygen of 6.5% volume, the carbon dioxide of 5% volume, the nitrogen of 4.7% volume, the argon gas of 5.5% volume, the ethane of 0.3% volume, the chloroethanes of 4.8vpm, and all the other are methane.Constantly fresh components, especially fresh ethylene and the oxygen of postreaction entraining air stream remain unchanged with the composition of keeping described air-flow in process of production.Bundle of reaction tubes is immersed in the water that is superheated to 210 ℃ (saturation temperatures).Measure the temperature of reactive gas current along reaction tube.Mark and draw the function curve (1) of gas flow temperature according to curve map shown in Figure 5 as the length of the pipe (5) that originates in inlet (6).
Carry out five tests under the described conditions, each test all changes the importing speed of the fresh components of reactive gas current, especially the importing speed of fresh ethylene and oxygen is to obtain corresponding oxirane output (P) (representing with ton oxirane/sky), and, calculate the selectivity (S) (representing) of reacting ethylene oxide according to above-mentioned equation (1) with % to each output (P).Described test the results are shown in table 1 and with this according to chart plot curve shown in Figure 6 (1), set forth the relation of selectivity (S) and oxirane output (P).
Table 1: the functional relation of selectivity (S) and oxirane output (P)
| | Test | Selectivity (S) (%) | Output (P) (t/d) |
| 1 | 83.2 | 256 | |
| 2 | 82.1 | 275 | |
| 3 | 81.0 | 290 | |
| 4 | 79.8 | 302 | |
| 5 | 78.5 | 314 |
Adopt the process identical with embodiment 1, different is that tubular reactor comprises a branch of 2760 cylindrical reaction tubes (5) (mutually the same and parallel).Each reaction tube (5) comprises two continuous levels (9) as shown in Figure 3, so this Guan Yousan continuous and adjoin cylindrical tubular zone (10) composition, and each described zone length is that L and its internal diameter (Di) reduce between inlet (6) and outlet (7).The length (L) in continuous three zones (10) between tube inlet (6) and outlet (7) and the value of internal diameter (Di) are as follows: L=5m and Di=64.0mm; L=5m and Di=38.4mm; L=2m and Di=25.6mm.Fill in the reaction tube as embodiment 1 described argentum-based catalyzer, the filling mode of each pipe is identical and all almost occupy full pipe range (96%).The cumulative volume and the embodiment 1 of the catalyst of the reaction tube of introducing reactor are described identical.
Carry out three tests under the described conditions, each test all changes the importing speed of the fresh components of reactive gas current, especially the importing speed of fresh ethylene and oxygen is to obtain corresponding oxirane output (P) (representing with ton oxirane/sky), and, calculate the selectivity (S) (representing) of reacting ethylene oxide according to above-mentioned equation (1) with % to each output (P).Described test the results are shown in table 2 and with this according to chart plot curve shown in Figure 6 (2), set forth the relation of selectivity (S) and oxirane output (P).
Table 2: the functional relation of selectivity (S) and oxirane output (P)
| | Test | Selectivity (S) (%) | Output (P) (t/d) |
| 1 | 81.7 | 277 | |
| 2 | 80.4 | 299 | |
| 3 | 78.9 | 315 |
Embodiment 3 (comparison)
Adopt the process identical with embodiment 1, different is that tubular reactor comprises a branch of 4750 cylindrical reaction tubes (5) (mutually the same and parallel).Each reaction tube (5) has conventional shape, and its internal diameter (Di) keeps constant and equals 38.7mm between tube inlet (6) and outlet (7).Pipe range (L) is 12m.Fill in the reaction tube as embodiment 1 described money base carried catalyst, the filling mode of each pipe is identical and all occupy almost pipe range (96%) entirely.The cumulative volume and the embodiment 1 of the catalyst of the reaction tube of introducing reactor are described identical.
Measure the temperature of reactive gas current along reaction tube.Mark and draw the function curve (2) of gas flow temperature according to curve map shown in Figure 5 as the length of the pipe (5) that originates in inlet (6).
Carry out five comparative tests under the described conditions, each test all changes the importing speed of the fresh components of reactive gas current, especially the importing speed of fresh ethylene and oxygen is to obtain corresponding oxirane output (P) (representing with ton oxirane/sky), and, calculate the selectivity (S) (representing) of reacting ethylene oxide according to above-mentioned equation (1) with % to each output (P).Described test the results are shown in table 3 and with this according to chart plot curve shown in Figure 6 (3), set forth the relation of selectivity (S) and oxirane output (P).
Table 3: the functional relation of selectivity (S) and oxirane output (P)
| Embodiment 3 (comparison) | Test | Selectivity (S) (%) | Output (P) (t/d) |
| 1 | 83.8 | 235 | |
| 2 | 82.8 | 248 | |
| 3 | 81.8 | 257 | |
| 4 | 80.8 | 266 | |
| 5 | 79.7 | 275 |
Tracing analysis is as follows shown in table 1,2 and 3 result and Fig. 5 and 6:
(a) according to method of the present invention, along the reaction temperature profile (Fig. 5 curve (1)) of pipe between tube inlet and the outlet with the popular response pipe on Temperature Distribution (Fig. 5 curve (2)) compare relatively stable; Therefore according to the present invention, rise rapidly and reach the initial temperature of catalytic reaction of synthesize epoxyethane rapidly in tube inlet district temperature; This afterreaction constantly rises and reaches the highest near 250 ℃, drop to about 215 ℃ then slightly, especially at the pipe outlet area, this makes service condition also make catalyst be continued to produce oxirane with good selectivity simultaneously away from the maximum combustion zone of admixture of gas;
(b) under the identical situation of all conditions, adopt method of the present invention, the selectivity (S) of the reacting ethylene oxide of given oxirane output (P) (Fig. 6 curve (1) and (2)) is higher than the selectivity (S) (Fig. 6 curve (3)) that obtains according to conventional method.
Claims (19)
1. one kind is utilized ethene and the molecular oxygen method that catalytic oxidation is produced oxirane in tubular reactor, this tubular reactor comprises three continuous and adjoin cavitys, the reactive gas current that contains ethene and molecular oxygen is crossed described cavity, a reactive gas current entrance cavity, be a center cavity subsequently, formation comprises the reaction product stream of oxirane, with a product gas flow outlet plenum, center cavity comprises a branch of reaction tube, described reaction tube is dipped in the heat exchanger fluid and is filled with solid silver-based catalyst, reactive gas current contacts with described catalyst and forms oxirane, each reaction tube comprises an inlet and an outlet of stretching into outlet plenum of stretching into entrance cavity, described method is characterised in that cross-sectional area reduces in the reaction tube of at least a portion pipe range between the reaction tube entrance and exit, and what surplus part in office described in cross-sectional area keep constant.
2. the method for claim 1, described method is characterised in that the interior cross-sectional area of reaction tube reduces continuously.
3. the method for claim 1, described method is characterised in that discontinuous the reducing of interior cross-sectional area of reaction tube, preferably reduces by level.
4. each method in the claim 1 to 3, described method are characterised in that the interior cross-sectional area (A1) of reaction tube inlet is bigger 1.5 to 12 times than the interior cross-sectional area (A2) of described pipe outlet, preferred 2 to 10 times, and more especially 3 to 9 times.
5. each method in the claim 1 to 4, described method is characterised in that the minimizing of cross-sectional area in the reaction tube only takes place once in the length of pipe, described reducing reduces on a part of length of pipe continuously, or discontinuous reducing, preferably reduce by level, described minimizing may betide the back segment of pipe range, but before last 1/5th sections of pipe outlet.
6. each method in the claim 1 to 4, described method is characterised in that in the reaction tube that the minimizing of cross-sectional area is recurred twice or repeatedly in pipe range, described reducing reduces in two or more partial continuous of pipe range, or discontinuous reducing, preferably reduce with two or more continuous levels, described minimizing betides the back segment of pipe range for the first time, but before last 1/5th sections of pipe outlet.
7. each method in the claim 1 to 6, described method are characterised in that the length (L) of reaction tube is 6 to 20m, preferred 8 to 15m, and cross-sectional area (Al) is 12 to 80cm in the reaction tube inlet
2, preferred 16 to 63cm
2, cross-sectional area (A2) is less than Al and be 1.2 to 16cm in the reaction tube outlet
2, preferred 1.8 to 12cm
2
8. each method in the claim 1 to 7, described method is characterised in that reaction tube is cylindrical and has cross section in the annular, its internal diameter (Di) reduces at least a portion of the pipe range from tube inlet to outlet, and what surplus part internal diameter in office keeps constant.
9. the method for claim 8, described method are characterised in that reaction tube inlet internal diameter (D1i) is bigger 1.2 to 3.5 times than described pipe outlet internal diameter (D2i), preferred 1.4 to 3.1 times, and more especially 1.7 to 3 times.
10. the method for claim 8, described method is characterised in that the length (L) of reaction tube is 6 to 20m, preferred 8 to 15m, reaction tube is 38 to 100mm at the internal diameter (D1i) of tube inlet, be preferably 45 to 90mm, the internal diameter (D2i) of pipe outlet, in D1i and be 12 to 45mm, be preferably 15 to 40mm.
11. each method in the claim 1 to 10, described method are characterised in that the thickness of reaction tube tube wall arrives between the outlet constant at tube inlet.
12. each method in the claim 1 to 10, described method are characterised in that the thickness of reaction tube tube wall changes between the outlet at tube inlet.
13. the external diameter that each method in the claim 8 to 10, described method are characterised in that reaction tube at tube inlet to constant between the outlet and preferably equal the external diameter of described tube inlet.
14. each method in the claim 1 to 13, described method are characterised in that the heat-exchange fluid that is used to immerse bundle of reaction tubes is selected from pressurization superheated water and organic heat transport fluid, preferred oils or hydrocarbon mixture.
15. the method for claim 14, described method are characterised in that organic heat transport fluid 100 to 1500kPa, preferred 200 to 800kPa, be more particularly 200 to 600kPa relative pressure use down.
16. the method for claim 14, described method are characterised in that superheated water uses under 1500 to 1800kPa relative pressure.
17. each method in the claim 1 to 16, described method are characterised in that the temperature of reactive gas current is selected from 140 to 350 ℃ in the reaction tube, preferred 180 to 300 ℃, are more particularly 190 to 280 ℃.
18. each method in the claim 1 to 17, described method are characterised in that reactive gas current is preheating to 100 to 200 ℃, preferred 140 to 190 ℃.
19. each method in the claim 1 to 18, described method is characterised in that the maximum temperature that the temperature maintenance reactive gas current of the reaction generation air-flow of reaction tube outlet is obtained or preferably is reduced to and is equal to or less than 250 ℃ in reaction tube, preferred 240 ℃, more especially 230 ℃, particularly be selected from 180 to 250 ℃, preferred 190 to 240 ℃, 200 to 230 ℃ temperature more especially.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0216145 | 2002-12-19 | ||
| FR0216145A FR2849031A1 (en) | 2002-12-19 | 2002-12-19 | Manufacture of ethylene oxide by the catalytic oxidation of ethylene with molecular oxygen in a tubular reactor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1747782A true CN1747782A (en) | 2006-03-15 |
Family
ID=32406186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200380109763.XA Pending CN1747782A (en) | 2002-12-19 | 2003-12-03 | Process for manufacturing ethylene oxide |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060054314A1 (en) |
| EP (1) | EP1572342A1 (en) |
| CN (1) | CN1747782A (en) |
| AU (1) | AU2003290219A1 (en) |
| FR (1) | FR2849031A1 (en) |
| NO (1) | NO20053400L (en) |
| WO (1) | WO2004056463A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102022943A (en) * | 2010-12-15 | 2011-04-20 | 茂名重力石化机械制造有限公司 | Heat exchange tube of tube type heat exchanger and tube type heat exchanger thereof |
| CN102744017A (en) * | 2011-04-22 | 2012-10-24 | 气体产品与化学公司 | Tubular reactor with jet impingement heat transfer |
| CN102921355A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Multitubular fixed bed reactor and coal bed methane deoxidation method |
| CN107107016A (en) * | 2014-11-14 | 2017-08-29 | 赛贝克环球科技公司 | Fixed bed reactors and its correlation technique |
| CN110494210A (en) * | 2017-02-08 | 2019-11-22 | 联邦科学和工业研究组织 | Isothermal reactor |
| CN113028864A (en) * | 2021-02-26 | 2021-06-25 | 南通星球石墨股份有限公司 | Preparation method of graphite impregnated tetrafluoro shell and tube heat exchanger |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1621247A1 (en) * | 2004-07-30 | 2006-02-01 | MAN DWE GmbH | Carry out of exothermic gas-phase reactions |
| BRPI0608862A2 (en) * | 2005-03-22 | 2010-02-02 | Shell Int Research | ethylene oxide reactor system and process |
| GB0509747D0 (en) * | 2005-05-13 | 2005-06-22 | Ashe Morris Ltd | Variable volume heat exchangers |
| MX2008007936A (en) | 2005-12-19 | 2008-09-24 | Bp Exploration Operating | Process for producing condensed-phase product from one or more gas-phase reactants. |
| US20080286159A1 (en) * | 2006-09-15 | 2008-11-20 | Grover Bhadra S | Variable Tube Diameter For SMR |
| US8569527B2 (en) | 2007-05-18 | 2013-10-29 | Shell Oil Company | Reactor system, an absorbent and a process for reacting a feed |
| WO2009116977A2 (en) | 2007-12-18 | 2009-09-24 | Dow Technology Investments Llc | Tube reactor |
| US20100139902A1 (en) * | 2008-12-05 | 2010-06-10 | Baylis Bobbye K | Plastic heat exchanger |
| US11504814B2 (en) | 2011-04-25 | 2022-11-22 | Holtec International | Air cooled condenser and related methods |
| WO2012149057A1 (en) * | 2011-04-25 | 2012-11-01 | Holtec International, Inc. | Air-cooled heat exchanger and system and method of using the same to remove waste thermal energy from radioactive materials |
| CN102865757B (en) * | 2012-08-31 | 2015-03-11 | 大连葆光节能空调设备厂 | Heat exchanger special for sewage source heat pump |
| CN102865758B (en) * | 2012-08-31 | 2015-03-11 | 大连葆光节能空调设备厂 | Heat exchanger special for sewage source thermal pump |
| CN102865694B (en) * | 2012-08-31 | 2015-03-11 | 大连葆光节能空调设备厂 | Heat exchanger special for sewage water source heat pump |
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| CN105705229B (en) | 2013-11-07 | 2018-05-01 | 株式会社日本触媒 | Reaction tube filler, reaction tube and the reaction method for having used the reaction tube |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2929300A1 (en) * | 1979-07-19 | 1981-01-29 | Linde Ag | Reactor for heterogeneous catalyst gas phase reactions - is cross sectionally tailored to specific heat requirements in different reaction stages |
| US7316804B2 (en) * | 2001-08-02 | 2008-01-08 | Ineos Usa Llc | Flow reactors for chemical conversions with heterogeneous catalysts |
-
2002
- 2002-12-19 FR FR0216145A patent/FR2849031A1/en not_active Withdrawn
-
2003
- 2003-12-03 CN CN200380109763.XA patent/CN1747782A/en active Pending
- 2003-12-03 AU AU2003290219A patent/AU2003290219A1/en not_active Abandoned
- 2003-12-03 EP EP03782582A patent/EP1572342A1/en not_active Withdrawn
- 2003-12-03 WO PCT/GB2003/005203 patent/WO2004056463A1/en not_active Application Discontinuation
- 2003-12-03 US US10/539,412 patent/US20060054314A1/en not_active Abandoned
-
2005
- 2005-07-13 NO NO20053400A patent/NO20053400L/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102022943A (en) * | 2010-12-15 | 2011-04-20 | 茂名重力石化机械制造有限公司 | Heat exchange tube of tube type heat exchanger and tube type heat exchanger thereof |
| CN102022943B (en) * | 2010-12-15 | 2013-01-30 | 茂名重力石化机械制造有限公司 | Heat exchange tube of tube type heat exchanger and tube type heat exchanger thereof |
| CN102744017A (en) * | 2011-04-22 | 2012-10-24 | 气体产品与化学公司 | Tubular reactor with jet impingement heat transfer |
| CN102744017B (en) * | 2011-04-22 | 2014-11-12 | 气体产品与化学公司 | Tubular reactor with jet impingement heat transfer |
| CN102921355A (en) * | 2011-08-08 | 2013-02-13 | 中国石油化工股份有限公司 | Multitubular fixed bed reactor and coal bed methane deoxidation method |
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| CN107107016A (en) * | 2014-11-14 | 2017-08-29 | 赛贝克环球科技公司 | Fixed bed reactors and its correlation technique |
| CN110494210A (en) * | 2017-02-08 | 2019-11-22 | 联邦科学和工业研究组织 | Isothermal reactor |
| CN110494210B (en) * | 2017-02-08 | 2022-03-18 | 联邦科学和工业研究组织 | Isothermal reactor |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2004056463A1 (en) | 2004-07-08 |
| NO20053400D0 (en) | 2005-07-13 |
| EP1572342A1 (en) | 2005-09-14 |
| AU2003290219A1 (en) | 2004-07-14 |
| FR2849031A1 (en) | 2004-06-25 |
| US20060054314A1 (en) | 2006-03-16 |
| NO20053400L (en) | 2005-09-19 |
| AU2003290219A8 (en) | 2004-07-14 |
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