CN114459263A - Heat exchanger, butylene oxidative dehydrogenation device and method for preparing butadiene through butylene oxidative dehydrogenation - Google Patents
Heat exchanger, butylene oxidative dehydrogenation device and method for preparing butadiene through butylene oxidative dehydrogenation Download PDFInfo
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- CN114459263A CN114459263A CN202011132954.XA CN202011132954A CN114459263A CN 114459263 A CN114459263 A CN 114459263A CN 202011132954 A CN202011132954 A CN 202011132954A CN 114459263 A CN114459263 A CN 114459263A
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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
- F28D7/0066—Multi-circuit heat-exchangers, e.g. integrating different heat exchange sections in the same unit or heat-exchangers for more than two fluids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
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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
- F28F9/00—Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
- F28F9/001—Casings in the form of plate-like arrangements; Frames enclosing a heat exchange core
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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
- F28F9/00—Casings; Header boxes; Auxiliary supports for elements; Auxiliary members within casings
- F28F9/22—Arrangements for directing heat-exchange media into successive compartments, e.g. arrangements of guide plates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention discloses a heat exchanger, a butylene oxidative dehydrogenation device and a method for preparing butadiene through butylene oxidative dehydrogenation. The heat exchanger comprises a shell, a hot material flow inlet, a hot material flow outlet, a gas-phase cold material flow inlet, a liquid-phase cold material flow inlet and a cold material flow outlet which are arranged on the surface of the shell, and a heat exchange tube and a shell space which are arranged inside the shell; heat exchange is performed between the hot stream, the gas-phase cold stream and the liquid-phase cold stream in the shell; the housing includes a connected horizontally disposed cylinder and a rectangle above the cylinder. When the heat exchanger is used for gas-liquid two-phase heat exchange, the gas-liquid two-phase heat exchanger can realize uniform distribution of the gas-liquid two-phase heat exchange and has a good heat exchange effect. The heat exchanger is used for preparing butadiene by oxidative dehydrogenation of butylene, and has the advantages of low system energy consumption, small steam consumption, no influence on a reaction system, low equipment investment and simple and convenient control.
Description
Technical Field
The invention relates to a heat exchanger, a butylene oxidative dehydrogenation device and a method for preparing butadiene through butylene oxidative dehydrogenation.
Background
Butadiene is an important monomer for synthetic rubber and synthetic resin, and is mainly used for synthesizing butadiene rubber, styrene butadiene rubber, nitrile butadiene rubber, ABS resin and the like. Butadiene is also a raw material for various coatings and organic chemicals.
At present, the production modes of butadiene mainly comprise four-carbon fraction separation and synthesis methods (including butane dehydrogenation, butene oxidative dehydrogenation and the like). At present, except the United states, almost all of the butadiene in all countries of the world is directly from the carbon four fraction which is a byproduct in the preparation of ethylene by hydrocarbon cracking. The source of butadiene in the united states, about half from butane, butene dehydrogenation, and half directly from cracked carbon four cut. In recent years, with the change of energy structures, industries such as carbon-chemical industry and shale gas are rapidly developed, so that the yield of butadiene from cracking carbon four-fraction is gradually reduced, and a method for preparing butadiene by oxidative dehydrogenation of butylene is gradually developed and paid attention to.
The butylene oxidative dehydrogenation reaction is to convert butylene into butadiene through oxidative dehydrogenation of oxygen under the action of a catalyst, the obtained main reaction product is butadiene, and the side reaction products comprise oxygen-containing compounds such as carbon dioxide, carbon monoxide, furan, aldonic acid and the like. The existing reactor is mainly an adiabatic fixed bed, generally a multi-section adiabatic fixed bed, butylene, water and oxygen-containing gas are used as raw materials, and as the reaction heat release is large, a large amount of water vapor is generally required to be supplemented to control the temperature of a catalyst bed layer within a proper range, so that the process energy consumption is high. For this reason, various patents have proposed various methods for recovering the heat of the oxidative dehydrogenation of butene and reducing the amount of steam used.
For example, CN101367702A discloses a method for preparing butadiene by oxidative dehydrogenation of butene in an axial fixed bed, wherein butadiene is prepared by using butene, air and steam as raw materials in two axial fixed beds, wherein an intersegment heat exchanger is arranged between the two axial fixed beds, and heat is recovered by heating the steam feed of the first axial fixed bed by using the discharge of the first axial fixed bed. However, the heat at the outlet of the secondary reactor of this process is not efficiently recovered.
CN107986930A discloses a process method for preparing butadiene by oxidative dehydrogenation of butylene through a three-section adiabatic fixed bed reaction system, wherein a waste heat boiler is added behind each section of fixed bed reactor, the heat of the reaction system is recovered, and steam is generated for recycling, so that the steam consumption is effectively reduced. However, this method requires a large amount of additional equipment, and thus has a problem of large equipment investment.
CN105042880A discloses a three-stage recovery process for heat of generated gas of butylene oxidative dehydrogenation reaction, wherein the generated gas is sequentially passed through a heat exchanger, a waste heat boiler and a heat pump system to recover heat, so that the heat above 80 ℃ can be effectively recovered, and although higher heat recovery rate can be realized, the method has more devices and is complex to control.
CN104974004A discloses a method for directly injecting water into a reactor steam system to save steam and reduce wastewater, in which water and steam are mixed in a steam-water mixer and then enter a heat exchanger to recover heat, but the ratio of water to steam is not strictly limited, once an unstable gas-liquid two-phase flow is formed in a pipeline, pipeline vibration and heat transfer efficiency reduction of the heat exchanger are caused, which brings great difficulty to operation and equipment design, and in addition, the method still has the problems of more equipment, large pipeline pressure drop and complex control.
CN107867967A discloses a method for preparing butadiene by oxidative dehydrogenation of butene, which adopts a multi-stage adiabatic fixed bed reactor, introduces liquid water into the feeding materials between the second stage and the subsequent adiabatic fixed bed, and adds the liquid water between the stages only as a heat removal means, thus the steam consumption can not be effectively reduced, and the fluctuation of the inlet temperature of the two-stage reactor is easy to cause, and the performance of the catalyst is influenced.
CN105536654A discloses a large-scale axial multistage mixed heat exchange type butylene oxidation dehydrogenation reactor, a plurality of axial catalyst bed layers are arranged in the reactor, a mixture of butylene, air and water is added between the bed layers as a cold shock stream to cool materials, but the equipment structure is relatively complex, and the size of the reactor is large, the cold shock stream is difficult to be uniformly distributed, so that the temperature fluctuation of the bed layers is aggravated, and the side reactions of generating aldehyde, ketone and the like are increased.
CN103657536A discloses an axial and radial combined type fixed bed catalytic reactor for oxidative dehydrogenation of butene, wherein at least one axial reaction section, one radial reaction section and an inter-section chilling section are arranged in the reactor, chilling materials are a mixture of raw materials and water, and cooling and heat recovery of a reaction system are carried out through a chilling spray system. The problem of uneven distribution of the cold shock material flow is improved by the spraying device, but the problem of increased side reactions of aldehyde, ketone and the like is still unavoidable because the position of adding the liquid water is still between the sections of the reactor.
Therefore, in order to solve the above problems, it is urgently required to develop a butene oxidative dehydrogenation reaction method which has high heat recovery efficiency, uses less steam, and can fully recover heat without affecting a reaction system.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a novel heat exchanger which can realize the uniform distribution of gas-liquid two phases and has better heat exchange effect when the gas-liquid two-phase heat exchange is carried out. The heat exchanger is used for preparing butadiene by oxidative dehydrogenation of butylene, and has the advantages of low system energy consumption, small steam consumption, no influence on a reaction system, low equipment investment and simple and convenient control.
The invention provides a heat exchanger in a first aspect, which comprises a shell, a hot material flow inlet, a hot material flow outlet, a gas-phase cold material flow inlet, a liquid-phase cold material flow inlet and a cold material flow outlet which are arranged on the surface of the shell, and a heat exchange tube and a shell space which are arranged inside the shell; heat exchange is performed between the hot stream, the gas-phase cold stream and the liquid-phase cold stream in the shell; a hot stream enters said shell through a hot stream inlet and flows within said heat exchange tubes and out of a hot stream outlet; the gas-phase cold material flow enters the shell through a gas-phase cold material flow inlet, flows in the shell space inside the shell and flows out of a cold material flow outlet; the liquid phase cold material flow enters the shell through the liquid phase cold material flow inlet, flows in the shell space inside the shell and flows out of the cold material flow outlet; the housing includes a connected horizontally disposed cylinder and a rectangle above the cylinder.
According to some embodiments of the heat exchanger of the present invention, the ratio of the height of the rectangle to the diameter of the cylinder is 0.1-0.5: 1. for example, 0.1: 1. 0.2: 1. 0.3: 1. 0.4: 1. 0.5: 1, and any value in between.
According to some embodiments of the heat exchanger of the present invention, the heat exchanger is further provided with a liquid distributor inside the shell and at the liquid-phase cold stream inlet. In the present invention, the number of the liquid distributors may be one or more, and may be determined as needed.
According to some embodiments of the heat exchanger of the present invention, the liquid distributor comprises a liquid-phase cold material flow inlet header pipe, a plurality of branch pipes distributed in a tree shape, and small holes arranged along the axial direction of the last branch pipe. The liquid phase cold material flow enters the liquid phase cold material flow inlet main pipe, then flows into the multi-stage branch pipes which are distributed in a tree-like shape, flows out through the small holes which are axially arranged on the last stage branch pipe, and enters the shell space of the heat exchanger.
According to some embodiments of the heat exchanger of the present invention, the number of stages of the multi-stage branch pipes may be determined as desired, for example, five-stage branch pipes (first stage branch pipe, second stage branch pipe, third stage branch pipe, fourth stage branch pipe, fifth stage branch pipe), as shown in fig. 2.
According to some embodiments of the heat exchanger of the present invention, the subsequent stage branch pipe is disposed perpendicular to the previous stage branch pipe.
According to some embodiments of the heat exchanger of the present invention, the ratio of the diameter of the next stage branch pipe to the diameter of the previous stage branch pipe is 0.5 to 1: 1, e.g. 0.5: 1. 0.6: 1. 0.7: 1. 0.8: 1. 0.9: 1. 1: 1, and any value in between. Preferably 0.6 to 0.8: 1.
according to some embodiments of the heat exchanger of the present invention, the ratio of the diameter of the small hole to the diameter of the last stage branch pipe is 0.01 to 0.5: 1. for example, 0.01: 1. 0.1: 1. 0.2: 1. 0.3: 1. 0.4: 1. 0.5: 1, and any value in between.
According to some embodiments of the heat exchanger of the present invention, the aperture ratio of the small hole on the last stage branch pipe is 5 to 30%. Such as 5%, 10%, 15%, 20%, 25%, 30%, and any value in between.
According to some embodiments of the heat exchanger according to the invention, the direction of the opening of the small hole in the last stage branch is at an angle of-90 ° to 90 °, preferably 0 ° to 90 °, more preferably 0 ° to 75 °, more preferably 0 ° to 60 ° to the horizontal. Taking the horizontal plane as a reference, the downward direction is a positive value, and the upward direction is a negative value. For example 90 deg. means vertically downwardly opening.
According to some embodiments of the heat exchanger according to the invention, the gas phase cold stream is fed into the shell and the heat exchanger is provided with a gas distributor. In the present invention, the number of the gas distributors may be one or more, and may be determined as needed.
According to some embodiments of the heat exchanger of the present invention, the gas distributor is a single stage baffle distributor.
According to some embodiments of the heat exchanger of the present invention, the baffle is a flat plate single stage baffle or a conical single stage baffle.
According to some embodiments of the heat exchanger of the present invention, the heat exchanger further comprises a hot stream inlet head and a hot stream outlet head. The material flow enters the heat exchange tube from the connecting tube of the hot material flow inlet end socket, flows in the heat exchange tube and flows out of the shell from the outlet tube of the hot material flow outlet end socket.
According to some embodiments of the heat exchanger of the present invention, the outer diameter, length, number and the like of the heat exchange tubes have a wide selection range, which can be determined according to needs.
According to some embodiments of the heat exchanger according to the invention, the diameter of the gas phase cold stream inlet has a wide range of options, which can be determined as desired.
According to some embodiments of the heat exchanger according to the invention, the diameter of the liquid phase cold stream inlet has a wide range of options, which can be determined as desired.
The invention provides a butene oxidative dehydrogenation device, which comprises at least two sections of fixed bed reactors connected in series or in parallel, wherein the outlet of each section of reactor is provided with the heat exchanger. And water vapor and supplementary condensate are respectively introduced into the shell space of the heat exchanger from the gas-phase cold material flow inlet and the liquid-phase cold material flow inlet and exchange heat with reaction generated gas introduced into the heat exchange tubes of the heat exchanger from the hot material flow inlet, the generated water vapor exchanges heat with the next section of supplementary condensate and the reaction generated gas in the heat exchanger at the outlet of the next section of reactor, and the process is repeated until the last section of reactor.
The third aspect of the invention provides a method for preparing butadiene by oxidative dehydrogenation of butylene, which comprises the following steps:
a) at least two sections of fixed bed reactors connected in series or in parallel are adopted;
b) the heat exchanger is arranged at the outlet of each section of the reactor, water vapor is used as a gas-phase cold material flow, a supplementary condensate is used as a liquid-phase cold material flow, and reaction generated gas flowing out of the reactor is used as a hot material flow; respectively introducing the metered water vapor and the supplemented condensate into the shell space of the heat exchanger from the gas-phase cold material flow inlet and the liquid-phase cold material flow inlet, exchanging heat with the reaction generated gas introduced into the heat exchange tube of the heat exchanger from the hot material flow inlet, exchanging heat between the generated water vapor and the next segment of supplemented condensate and the reaction generated gas in the heat exchanger at the outlet of the next segment of reactor, and repeating the process until the last segment of reactor;
c) introducing the water vapor at the cold flow outlet of the heat exchanger at the outlet of the last section of reactor, the metered butene used in the first section and the oxygen-containing gas into the first section of reactor to perform butene oxidative dehydrogenation;
d) and (3) introducing the effluent of the hot effluent outlet of the heat exchanger at the outlet of each section of reactor, the butene used in the next section and the oxygen-containing gas which are respectively metered into the reactor in the next section till the reactor in the last section to obtain the butadiene product.
According to some embodiments of the process of the present invention, the molar ratio of butene, oxygen-containing gas as oxygen, and water vapor at the inlet of each stage of the reactor is independently 1: 0.3-0.8: 10-30, preferably 1: 0.4-0.6: 15-25.
According to some embodiments of the process of the present invention, the reaction conditions within each stage of the reactor independently comprise: the pressure is from 0 to 1000kPa, preferably from 0 to 500 kPa.
According to some embodiments of the process of the present invention, the reaction conditions within each stage of the reactor independently comprise: the temperature is 250-600 ℃, preferably 300-500 ℃.
According to some embodiments of the method of the present invention, the condensate is evaporative condensate and/or boiler circulating water.
According to some embodiments of the method of the present invention, the temperature of the condensate is 20 to 200 ℃.
According to some embodiments of the method of the present invention, the oxygen-containing gas is selected from air and/or pure oxygen.
According to some embodiments of the process of the present invention, the steam enters the heat exchangers at the outlet of the reactors of each stage in sequence or in reverse order. Such as shown in fig. 3 and 4. Wherein, FIG. 3 is a heat exchanger for water vapor entering the outlet of each reactor section in sequence, and FIG. 4 is a heat exchanger for water vapor entering the outlet of each reactor section in reverse sequence
According to some embodiments of the method of the present invention, the fixed bed reactor is a multi-stage adiabatic fixed bed reactor.
According to some embodiments of the process of the present invention, a two-stage series-parallel adiabatic fixed bed is used, wherein the flow rate of the first stage make-up condensate is 2-25 wt% of the main steam flow rate, and the flow rate of the second stage make-up condensate is 5-35 wt% of the main steam flow rate.
According to some embodiments of the method of the present invention, a three-stage series-parallel adiabatic fixed bed is used, wherein the flow rate of the first stage make-up condensate accounts for 2-20 wt% of the main steam flow rate, the flow rate of the second stage make-up condensate accounts for 5-30 wt% of the main steam flow rate, and the flow rate of the third stage make-up condensate accounts for 0.1-8 wt% of the main steam flow rate.
According to some embodiments of the method of the present invention, four or more sections of adiabatic fixed beds connected in series and in parallel are used, the flow rate of the first section of the supplementary condensate accounts for 2-20 wt% of the flow rate of the main steam, the flow rate of the second section of the supplementary condensate accounts for 5-20 wt% of the flow rate of the main steam, the flow rate of the third section of the supplementary condensate accounts for 5-15 wt% of the flow rate of the main steam, and the flow rates of the four or more sections of the supplementary condensate account for the flow rate of the main steam as required.
The inventors of the present invention found through research that: the proportion of the supplementary condensate to the main steam flow in each section is not too high or too low. If the proportion of the supplementary condensate is too high, the steam and the condensate are mixed to form gas-liquid two-phase material flow, so that pipeline vibration and reduction of heat transfer efficiency of a heat exchanger are easily caused, and great difficulty is brought to operation and equipment design. If the proportion of the supplementary condensate is too low, the steam temperature is too high and is not enough to cool the temperature of the reaction generated gas to the temperature required by the inlet of the next section of reactor, so that the inlet temperature of the bed layer of the reactor is increased, the performance of the catalyst is influenced, and the reaction selectivity and the conversion rate are reduced. Therefore, for the fixed bed reactors connected in series or in parallel in different stages, the ratio of the supplementary condensate to the main steam flow rate in each stage is preferably performed under the above conditions.
The invention has the beneficial effects that:
(1) compared with a mode of recovering heat by a boiler, the heat exchanger has high heat recovery efficiency and less equipment investment.
(2) In the preferable situation of the invention, when the liquid distributor and the gas distributor are arranged in the heat exchanger, compared with the mixing mode of water and steam in the pipeline, the invention uniformly distributes the water and the steam, avoids forming unstable gas-liquid two-phase flow in the pipeline and greatly improves the operation safety and the stability.
(3) The shell of the heat exchanger comprises the horizontally placed cylinder and the rectangle above the cylinder, which are communicated, and the heat exchange efficiency can be improved on the basis of not influencing the design structure of the original heat exchanger.
(4) The liquid distributor disclosed by the invention has the advantages of reduced pressure, uniform distribution and the like.
(5) According to the device and the method for preparing butadiene through oxidative dehydrogenation of butene, condensate and water vapor are mixed before entering a reaction system, and the condensate is directly used as a vapor raw material after being vaporized and enters a first-stage reactor completely, so that the amount of fed vapor is greatly reduced, and the problem of increase of side reactions for generating aldehyde, ketone and the like caused by intersegmental condensation is solved.
(6) If according to the methods provided by CN107867967A, CN105536654A, and CN103657536A, chilled water is supplemented between the sections of the reaction catalyst bed, once the proportion is improperly controlled, the inlet temperature of the subsequent reactor is easily fluctuated, which affects the exertion of the catalyst activity, and also increases the risk of carbon deposition in the reactor. The device and the method of the invention avoid the problems by mixing the condensate and the steam in the reaction system, leading all the mixed superheated steam to enter the first-stage reactor, and leading the temperature of the superheated steam entering the first-stage reactor to be 300-500 ℃. Meanwhile, the temperature of the mixed fluid is controlled to be 100-400 ℃ in a cascade mode through the temperature of the mixed water vapor and each section of supplementary condensate and the flow of each section of supplementary condensate, so that the temperature of the steam entering the outlet heat exchangers of each section of reactor can be reduced, the heat transfer temperature difference is increased, and the heat recovery efficiency is higher.
Drawings
FIG. 1 is a schematic view of a heat exchanger provided in example 1 of the present invention;
FIG. 2 is a schematic view of a liquid distributor provided in example 1 of the present invention;
FIG. 3 is a schematic diagram of a process for preparing butadiene by oxidative dehydrogenation of butene according to example 2 of the present invention;
FIG. 4 is a schematic diagram of a process for preparing butadiene by oxidative dehydrogenation of butene according to example 4 of the present invention;
FIG. 5 is a schematic diagram of the procedure for preparing butadiene by oxidative dehydrogenation of butene in comparative example 1.
Description of the reference numerals
E1, hot material inlet E2, hot material inlet end socket E3 and hot material outlet
E4, hot material flow outlet end socket E5, gas phase cold material flow inlet E6 and cold material flow outlet
E7, shell space E8, heat exchange tube E9 and liquid-phase cold material flow inlet
E10, gas distributor E11, liquid distributor;
y1, liquid-phase cold material flow inlet manifold Y2, first-stage branch pipes Y3 and second-stage branch pipes
Y4, a third branch Y5, a fourth branch Y6 and a fifth branch
Y7, pinhole;
101. a first-stage reactor 102, a second-stage reactor 103, and a third-stage reactor
104. A first-stage outlet heat exchanger 105, a second-stage outlet heat exchanger 106, and a third-stage outlet heat exchanger
1. Butene total feed 2, oxygen-containing gas total feed 3, principal steam
4. Make-up condensate 5, first-stage butene feed 6, second-stage butene feed
7. Three-stage butene feed 8, first-stage oxygen-containing gas feed 9, second-stage oxygen-containing gas feed
10. Three-stage oxygen-containing gas feeding 11, first-stage supplementary condensate 12 and second-stage supplementary condensate
13. Three-stage supplementary condensate 14, a first reverse outlet material flow 15 and a second reverse outlet material flow
16. Three-stage supplementary condensate comprising three-stage outlet material flow 17, product material flow 18 and three-stage supplementary condensate
19. A second stage supplementary condensate 20 and a first stage supplementary condensate;
d101, a first-stage reactor D102, a second-stage reactor D103 and a second-stage outlet heat exchanger
D1, total butene feed D2, total oxygen-containing gas feed D3, and main steam
D4, interstage quench water D5, first stage butene feed D6, second stage butene feed
D7, primary oxygen-containing gas feed D8, secondary oxygen-containing gas feed D9, a back-off stream
D10, a double-outlet material flow D11 and a product material flow.
Detailed Description
In order that the present invention may be more readily understood, the following detailed description of the invention is given by way of example only, and is not intended to limit the scope of the invention.
[ example 1 ]
A heat exchanger, as shown in figure 1, comprises a shell, a hot material flow inlet E1, a hot material flow inlet end socket E2, a hot material flow outlet E3, a hot material flow outlet end socket E4, a gas phase cold material flow inlet E5, a liquid phase cold material flow inlet E9 and a cold material flow outlet E6 on the surface of the shell, and a heat exchange tube E8 and a shell space E7 in the interior of the shell; in the shell, heat exchange is carried out on the hot material flow, the gas-phase cold material flow and the liquid-phase cold material flow; the hot material flow enters the shell through the hot material flow inlet, flows in the heat exchange tube and flows out of the hot material flow outlet; the gas-phase cold material flow enters the shell through the gas-phase cold material flow inlet, flows in the shell space inside the shell and flows out of the cold material flow outlet; the liquid phase cold material flow enters the shell through the liquid phase cold material flow inlet, flows in the shell space inside the shell and flows out of the cold material flow outlet; the housing includes a connected horizontally disposed cylinder and a rectangle above the cylinder. The diameter of a cylinder (a cylindrical part) of a shell of the heat exchanger is 1200mm, the rectangular space above the cylinder is 2000mm long multiplied by 900mm wide multiplied by 400mm high, the outer diameter of the heat exchange tube is 38mm, the length is 6000mm, and the number of the heat exchange tubes is 495. The diameter of the gas phase cold material flow inlet E5 is 300mm, the gas phase cold material flow inlet E5 is two inlets which are symmetrically distributed, a gas distributor E10 is arranged below each inlet, and the gas distributor E10 is a single-stage baffle plate in a flat plate shape. The liquid phase cold material flow inlet E9 is 150mm in diameter, and a liquid distributor E11 is arranged at the liquid phase cold material flow inlet and inside the shell. The liquid distributor E11 is shown in FIG. 2 and located in the rectangular space, and comprises a liquid phase cold material flow inlet manifold Y1, five-stage branch pipes (a first-stage branch pipe Y2, a second-stage branch pipe Y3, a third-stage branch pipe Y4, a fourth-stage branch pipe Y5 and a fifth-stage branch pipe Y6) which are distributed in a tree shape, and small holes Y7 which are axially arranged on the fifth-stage branch pipes. The ratio of the diameter of the branch pipe at the next stage to the diameter of the branch pipe at the previous stage is 0.6-0.8: 1, the diameters of the first-stage branch pipe Y2, the second-stage branch pipe Y3, the third-stage branch pipe Y4, the fourth-stage branch pipe Y5 and the fifth-stage branch pipe Y6 are respectively 100mm, 75mm, 50mm, 36mm and 25mm, a small hole Y7 of 6mm is axially formed in the last-stage branch pipe, the angle between the hole forming direction and the vertical direction is 60 degrees, and the hole forming rate is 10 percent.
[ example 2 ]
A device for preparing butadiene by oxidative dehydrogenation of 5 ten thousand tons/year butylene (8000 hours of annual operation) adopts a three-stage process technology shown in figure 3, wherein 101 is a first-stage reactor, 102 is a second-stage reactor, 103 is a third-stage reactor, 104 is a first-stage outlet heat exchanger, 105 is a second-stage outlet heat exchanger, 106 is a third-stage outlet heat exchanger, 1 is total feed of butylene, 2 is total feed of oxygen-containing gas, 3 is main steam, 4 is supplementary condensate, 5 is first-stage butylene feed, 6 is second-stage butylene feed, 7 is third-stage butylene feed, 8 is first-stage oxygen-containing gas feed, 9 is second-stage oxygen-containing gas feed, 10 is third-stage oxygen-containing gas feed, 11 is first-stage supplementary condensate, 12 is second-stage supplementary condensate, 13 is third-stage supplementary condensate, 14 is a reverse outlet material flow, 15 is a second reverse outlet material flow, 16 is a third reverse outlet material flow, and 17 is a product stream.
The reactor is a radial fixed bed, the oxygen-containing gas adopts air, and the outlets of the three sections of reactors are respectively provided with a heat exchanger in the embodiment 1. Taking water vapor as a gas-phase cold material flow, supplementing condensate as a liquid-phase cold material flow, and taking reaction generated gas flowing out of a reactor as a hot material flow; respectively introducing metered water vapor and supplementary condensate into a shell space of a heat exchanger from a gas-phase cold material flow inlet and a liquid-phase cold material flow inlet, exchanging heat with reaction generated gas introduced into a heat exchange tube of the heat exchanger from a hot material flow inlet, exchanging heat between the generated water vapor and the next supplementary condensate with the reaction generated gas in the heat exchanger at the outlet of the next reactor (the water vapor sequentially enters the heat exchanger at the outlet of each reactor), and repeating the process until the three reactors are completed; introducing water vapor at a cold material flow outlet of a heat exchanger at the outlet of the three-section reactor, and respectively metered butene and oxygen-containing gas used in the first section into the first section reactor to perform butene oxidative dehydrogenation; and (3) introducing the effluent of the hot effluent outlet of the heat exchanger at the outlet of each section of reactor, the butene used in the next section and the oxygen-containing gas which are respectively metered into the reactor in the next section till the reactor in the third section to obtain a butadiene product. The specific operating parameters are as follows:
the first stage reactor pressure was 220kPa (absolute), the feed temperature was 330 ℃, the total feed flow was 37500kg/hr, the feed composition was butene, the molar ratio of oxygen in the oxygen-containing gas to steam was 1: 0.42: 17.4; the second stage reactor pressure was 205kPa (absolute), the feed temperature was 340 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas and water vapor was 1: 0.49: 17.4; the three-stage reactor pressure was 190kPa (absolute), the feed temperature was 350 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas, and water vapor was 1: 0.56: 17.6. the main steam feed temperature was 148 deg.C, the pressure was 0.43MPa, and the flow rate was 21400 kg/hr. The temperature of the supplementary condensate is 145 ℃, the pressure is 0.45MPa, the supplementary condensate is supplemented in three sections, the supplementary condensate and the reaction product are subjected to heat exchange in a novel heat exchanger at the outlet of a three-section reactor to recover heat, wherein the flow rate of the supplementary condensate in one section is 1800kg/hr, the flow rate of the supplementary condensate in the second section is 3460kg/hr, the flow rate of the supplementary condensate in the third section is 750kg/hr, and the flow rate of the supplementary condensate in each section respectively accounts for 8.41 wt%, 16.17 wt% and 3.5 wt% of the flow rate of the water vapor.
The process has a steam to butene molar ratio of 8.54, a total steam demand of 27410kg/hr (steam demand ═ butene feed molar quantity × steam to butene molar ratio × molecular weight of water), with a practically used principal steam consumption of 21400kg/hr, and a steam savings of 6010kg/hr by means of supplementary condensate evaporation (steam savings ═ steam demand — actual principal steam demand), of 21.94% of the total steam consumed.
[ example 3 ]
A device for preparing butadiene by oxidative dehydrogenation of 5 ten thousand tons/year butylene (8000 hours of annual operation) adopts a three-stage process technology shown in figure 3, wherein 101 is a first-stage reactor, 102 is a second-stage reactor, 103 is a third-stage reactor, 104 is a first-stage outlet heat exchanger, 105 is a second-stage outlet heat exchanger, 106 is a third-stage outlet heat exchanger, 1 is total feed of butylene, 2 is total feed of oxygen-containing gas, 3 is main steam, 4 is supplementary condensate, 5 is first-stage butylene feed, 6 is second-stage butylene feed, 7 is third-stage butylene feed, 8 is first-stage oxygen-containing gas feed, 9 is second-stage oxygen-containing gas feed, 10 is third-stage oxygen-containing gas feed, 11 is first-stage supplementary condensate, 12 is second-stage supplementary condensate, 13 is third-stage supplementary condensate, 14 is a reverse outlet material flow, 15 is a second reverse outlet material flow, 16 is a third reverse outlet material flow, and 17 is a product stream.
The reactor is a radial fixed bed, the oxygen-containing gas adopts air, and the outlets of the three sections of reactors are respectively provided with a heat exchanger of the embodiment 1. Taking water vapor as a gas-phase cold material flow, supplementing condensate as a liquid-phase cold material flow, and taking reaction generated gas flowing out of a reactor as a hot material flow; respectively introducing metered water vapor and supplementary condensate into a shell space of a heat exchanger from a gas-phase cold material flow inlet and a liquid-phase cold material flow inlet, exchanging heat with reaction generated gas introduced into a heat exchange tube of the heat exchanger from a hot material flow inlet, exchanging heat between the generated water vapor and the next supplementary condensate with the reaction generated gas in the heat exchanger at the outlet of the next reactor (the water vapor sequentially enters the heat exchanger at the outlet of each reactor), and repeating the process until the three reactors are completed; introducing water vapor at a cold flow outlet of a heat exchanger at the outlet of the three-section reactor, and respectively metered butene and oxygen-containing gas used at the first section into the first section reactor to perform butene oxidative dehydrogenation; and (3) introducing the effluent of the hot effluent outlet of the heat exchanger at the outlet of each section of reactor, the butene used in the next section and the oxygen-containing gas which are respectively metered into the reactor in the next section till the reactor in the third section to obtain a butadiene product. The specific operating parameters are as follows:
the first stage reactor pressure was 220kPa (absolute), the feed temperature was 330 ℃, the total feed flow was 37500kg/hr, the feed composition was butene, the molar ratio of oxygen in the oxygen-containing gas to steam was 1: 0.42: 17.5; the second stage reactor pressure was 205kPa (absolute), the feed temperature was 340 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas and water vapor was 1: 0.49: 17.4; the three-stage reactor pressure was 190kPa (absolute), the feed temperature was 350 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas, and water vapor was 1: 0.56: 17.6. the main steam feed temperature was 148 deg.C, pressure 0.43MPa, and flow rate was 19785 kg/hr. The supplementary condensate temperature is 145 ℃, the pressure is 0.45MPa, and the supplementary condensate is supplemented in three sections, wherein the supplementary condensate in the first section is 1908kg/hr, the supplementary condensate in the second section is 5563kg/hr, the supplementary condensate in the third section is 222kg/hr, and the flow of the supplementary condensate in each section respectively accounts for 9.64 wt%, 28.12 wt% and 1.12 wt% of the flow of the steam.
The molar ratio of the water vapor to the butylene is 8.54, the total required steam amount is 27468kg/hr, wherein the actual main steam consumption is 19785kg/hr, and the steam saved by supplementary condensate evaporation is 7683kg/hr, which accounts for 28.00% of the total consumed steam.
[ example 4 ]
A device for preparing butadiene by oxidative dehydrogenation of 5 ten thousand tons/year butylene (8000 hours of annual operation) adopts a three-stage process technology shown in figure 4, wherein 101 is a first-stage reactor, 102 is a second-stage reactor, 103 is a third-stage reactor, 104 is a first-stage outlet heat exchanger, 105 is a second-stage outlet heat exchanger, 106 is a third-stage outlet heat exchanger, 1 is total feed of butylene, 2 is total feed of oxygen-containing gas, 3 is main steam, 4 is supplementary condensate, 5 is first-stage butylene feed, 6 is second-stage butylene feed, 7 is third-stage butylene feed, 8 is first-stage oxygen-containing gas feed, 9 is second-stage oxygen-containing gas feed, 10 is third-stage oxygen-containing gas feed, 18 is third-stage supplementary condensate, 19 is second-stage supplementary condensate, 20 is first-stage supplementary condensate, 14 is a reverse outlet material flow, 15 is a second reverse outlet material flow, 16 is a third reverse outlet material flow, and 17 is a product stream.
The reactor is a radial fixed bed, the oxygen-containing gas adopts air, and the outlets of the three sections of reactors are respectively provided with a heat exchanger in the embodiment 1. Taking water vapor as a gas-phase cold material flow, supplementing condensate as a liquid-phase cold material flow, and taking reaction generated gas flowing out of a reactor as a hot material flow; respectively introducing metered water vapor and supplementary condensate into a shell space of a heat exchanger from a gas-phase cold material flow inlet and a liquid-phase cold material flow inlet, exchanging heat with reaction generated gas introduced into a heat exchange tube of the heat exchanger from a hot material flow inlet, exchanging heat between the generated water vapor and the next supplementary condensate with the reaction generated gas in the heat exchanger at the outlet of the next reactor (the water vapor enters the heat exchanger at the outlet of each reactor in a reverse order), and repeating the process until the three reactors are formed; introducing water vapor at a cold flow outlet of a heat exchanger at the outlet of the three-section reactor, and respectively metered butene and oxygen-containing gas used at the first section into the first section reactor to perform butene oxidative dehydrogenation; and (3) introducing the effluent of the hot effluent outlet of the heat exchanger at the outlet of each section of reactor, the butene used in the next section and the oxygen-containing gas which are respectively metered into the reactor in the next section till the reactor in the third section to obtain a butadiene product. The specific operating parameters are as follows:
the first stage reactor pressure was 220kPa (absolute), the feed temperature was 330 ℃, the total feed flow was 37500kg/hr, the feed composition was butene, the molar ratio of oxygen in the oxygen-containing gas to steam was 1: 0.42: 17; the second stage reactor pressure was 205kPa (absolute), the feed temperature was 340 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas and water vapor was 1: 0.48: 17; the three-stage reactor pressure was 190kPa (absolute), the feed temperature was 350 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas, and water vapor was 1: 0.55: 18. the main steam feed temperature was 148 deg.C, the pressure was 0.43MPa, and the flow rate was 21400 kg/hr. The temperature of the supplementary condensate is 145 ℃, the pressure is 0.45MPa, the supplementary condensate is supplemented in three sections, the flow of the supplementary condensate in the three sections is adjusted to ensure that the temperature of the mixed water vapor and the supplementary condensate in the three sections is 280 ℃, the flow of the supplementary condensate in the two sections is adjusted to ensure that the temperature of the mixed water vapor and the supplementary condensate in the two sections is 300 ℃, and the flow of the supplementary condensate in the first section is adjusted to ensure that the feeding temperature of the reactor in the first section is 330 ℃. 2300kg/hr of first-stage supplementary condensate, 3300kg/hr of second-stage supplementary condensate and 430kg/hr of third-stage supplementary condensate, wherein the flow rate of each stage of supplementary condensate accounts for 10.75 wt%, 15.42 wt% and 2.01 wt% of the flow rate of the steam respectively.
The molar ratio of the water vapor to the butylene is 8.54, the total required steam amount is 27430kg/hr, the actual consumption of main steam is 21400kg/hr, and the steam saved by supplementary condensate evaporation 6030kg/hr accounts for 21.98% of the total consumed steam.
[ example 5 ]
A device for preparing butadiene by oxidative dehydrogenation of 5 ten thousand tons/year of butylene (8000 hours per year of operation), which is prepared according to the method of the embodiment 2, except that a two-stage process technology is adopted.
The reactor is a radial fixed bed, the oxygen-containing gas adopts air, and the outlets of the two sections of reactors are respectively provided with a heat exchanger of the embodiment 1. Taking water vapor as a gas-phase cold material flow, supplementing condensate as a liquid-phase cold material flow, and taking reaction generated gas flowing out of a reactor as a hot material flow; respectively introducing metered water vapor and supplementary condensate into a shell space of a heat exchanger from a gas-phase cold material flow inlet and a liquid-phase cold material flow inlet, exchanging heat with reaction generated gas introduced into a heat exchange tube of the heat exchanger from a hot material flow inlet, exchanging heat between the generated water vapor and the next supplementary condensate with the reaction generated gas in the heat exchanger at the outlet of the next reactor (the water vapor sequentially enters the heat exchanger at the outlet of each reactor), and repeating the process until reaching a second reactor; introducing water vapor at a cold material flow outlet of a heat exchanger at the outlet of the second-stage reactor, and respectively metered butene and oxygen-containing gas used in the first stage into the first-stage reactor for carrying out butene oxidative dehydrogenation; and (3) introducing the effluent of the hot effluent outlet of the heat exchanger at the outlet of each section of reactor, the butene used in the next section and the oxygen-containing gas which are respectively metered into the reactor in the next section till the reactor in the second section to obtain a butadiene product. The specific operating parameters are as follows:
the first stage reactor pressure was 255kPa (absolute), the feed temperature was 315 ℃, the total feed flow was 57500kg/hr, the feed composition was butene, the molar ratio of oxygen in the oxygen-containing gas to steam was 1: 0.58: 19; the second stage reactor pressure was 240kPa (absolute), the feed temperature was 350 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas and water vapor was 1: 0.58: 20. the main steam feed temperature was 148 deg.C, pressure 0.43MPa, and flow rate was 32000 kg/hr. The temperature of the supplementary condensate is 145 ℃, the pressure is 0.45MPa, the supplementary condensate is supplemented in two sections, the supplementary condensate and the reaction product exchange heat and recycle heat in a novel heat exchanger at the outlet of a second-section reactor respectively, wherein the flow rate of the supplementary condensate in one section is 3875kg/hr, the flow rate of the supplementary condensate in the second section is 2090kg/hr, and the flow rate of the supplementary condensate in each section respectively accounts for 12.11 wt% and 6.53 wt% of the flow rate of the water vapor.
The molar ratio of the water vapor to the butylene is 9.96, the total required steam amount is 37965kg/hr, wherein the actual consumption of the main steam is 32000kg/hr, and the steam saved by the evaporation of the supplementary condensate is 5965kg/hr, which accounts for 15.71% of the total consumed steam.
[ COMPARATIVE EXAMPLE 1 ]
A device for preparing butadiene by oxidative dehydrogenation of 5 ten thousand tons of butene per year (operation time per year is 8000 hours) adopts a two-stage process technology shown in figure 5, D101 is a first-stage reactor, D102 is a second-stage reactor, D103 is a second-stage outlet heat exchanger (the heat exchanger is a common two-way feeding tubular heat exchanger, tube side heat flow is a second-stage outlet flow D10, shell side cold flow is main steam D3), D1 is total feed of butene, D2 is total feed of oxygen-containing gas, D3 is main steam, D4 is interstage chilling water, D5 is first-stage butene feed, D6 is second-stage butene feed, D7 is first-stage oxygen-containing gas feed, D8 is second-stage oxygen-containing gas feed, D9 is first-stage outlet flow, D10 is second-stage outlet flow, and D11 is product flow.
The reactor is a radial fixed bed, and the oxygen-containing gas adopts air. The first stage reactor pressure was 255kPa (absolute), the feed temperature was 315 ℃, the total feed flow was 53100kg/hr, the feed composition was butene, the molar ratio of oxygen in the oxygen-containing gas to steam was 1: 0.58: 19; the second stage reactor pressure was 240kPa (absolute), the feed temperature was 350 ℃, and the feed composition was such that the molar ratio of butene, oxygen in the oxygen-containing gas and water vapor was 1: 0.58: 22. the main steam feed temperature was 148 deg.C, pressure 0.43MPa, and flow rate was 38000 kg/hr. The section is chilled by adopting a condensate, the temperature of the chilled condensate is 145 ℃, the pressure is 0.45MPa, and the flow rate is 4000 kg/hr.
The molar ratio of the water vapor to the butylene in the method is 11.8, the total required vapor amount is 42000kg/hr, wherein the actual consumption of the main vapor is 38000kg/hr, which is much higher than that in the embodiments 2-5 of the invention.
[ COMPARATIVE EXAMPLE 2 ]
The process of example 3 was followed except that the three heat exchangers of example 1 were replaced with a conventional two-feed shell and tube heat exchanger and the mixing point of the steam and condensate was placed before the shell and tube heat exchanger. The secondary supplement condensate is 5563kg/hr and accounts for 28.12 wt% of the flow of the steam. Because the proportion of the supplementary condensate is too high, unstable gas-liquid two-phase material flow is formed in the pipeline after the steam and the condensate are mixed, and the pipeline vibrates violently. Meanwhile, the gas phase and the liquid phase in the pipeline are extremely uneven in distribution when entering the heat exchanger, so that the heat transfer efficiency of the heat exchanger is reduced, the temperature of a hot material outlet is increased, and partial damage of the heat exchange pipe is found after the heat exchanger is stopped and overhauled.
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (10)
1. A heat exchanger comprising a shell, a hot stream inlet, a hot stream outlet, a vapor phase cold stream inlet, a liquid phase cold stream inlet, a cold stream outlet at the surface of the shell, and heat exchange tubes and shell space inside the shell; heat exchange is performed between the hot stream, the gas-phase cold stream and the liquid-phase cold stream in the shell;
a hot stream enters said shell through a hot stream inlet and flows within said heat exchange tubes and exits through a hot stream outlet;
the gas-phase cold material flow enters the shell through the gas-phase cold material flow inlet, flows in the shell space inside the shell and flows out of the cold material flow outlet;
the liquid phase cold material flow enters the shell through the liquid phase cold material flow inlet, flows in the shell space inside the shell and flows out of the cold material flow outlet;
the housing includes a connected horizontally disposed cylinder and a rectangle above the cylinder.
2. The heat exchanger according to claim 1, wherein the ratio of the height of the rectangle to the diameter of the cylinder is 0.1-0.5: 1.
3. the heat exchanger according to claim 1 or 2, wherein a liquid distributor is further provided inside the shell at the inlet of the liquid phase cold stream;
preferably, the liquid distributor comprises a liquid phase cold material flow inlet header pipe, a multi-stage branch pipe in dendritic distribution and small holes axially arranged in the last stage branch pipe;
more preferably, the rear-stage branch pipe is arranged perpendicular to the front-stage branch pipe;
more preferably, the ratio of the diameter of the branch pipe of the next stage to the diameter of the branch pipe of the previous stage is 0.5-1: 1, preferably 0.6 to 0.8: 1;
preferably, the ratio of the diameter of the small hole to the diameter of the branch pipe of the last stage is 0.01-0.5: 1,
more preferably, the aperture ratio of the small holes on the last stage branch pipe is 5-30%;
more preferably, the direction of the opening of the aperture in the last stage branch is at an angle of-90 ° to 90 °, preferably 0 ° to 90 °, more preferably 0 ° to 75 °, more preferably 0 ° to 60 ° to the horizontal.
4. The heat exchanger according to any one of claims 1 to 3, wherein a gas phase cold stream is introduced and inside the shell, the heat exchanger being further provided with a gas distributor;
preferably, the gas distributor is a single stage baffle distributor;
more preferably, the baffle is a flat plate single stage baffle or a conical single stage baffle.
5. A butene oxidative dehydrogenation apparatus comprising at least two stages of fixed bed reactors connected in series or in parallel, the heat exchanger of any one of claims 1 to 4 being provided at the outlet of each stage of the reactor.
6. A method for preparing butadiene by oxidative dehydrogenation of butylene comprises the following steps:
a) at least two sections of fixed bed reactors connected in series or in parallel are adopted;
b) arranging the heat exchanger as claimed in any one of claims 1 to 4 at the outlet of each reactor section, taking water vapor as a gas-phase cold material flow, supplementing condensate liquid as a liquid-phase cold material flow, and taking reaction product gas flowing out of the reactor as a hot material flow; respectively introducing the metered water vapor and the supplemented condensate into the shell space of the heat exchanger from the gas-phase cold material flow inlet and the liquid-phase cold material flow inlet, exchanging heat with the reaction generated gas introduced into the heat exchange tube of the heat exchanger from the hot material flow inlet, exchanging heat between the generated water vapor and the next segment of supplemented condensate and the reaction generated gas in the heat exchanger at the outlet of the next segment of reactor, and repeating the process until the last segment of reactor;
c) introducing the water vapor at the cold flow outlet of the heat exchanger at the outlet of the last section of reactor, the metered butene used in the first section and the oxygen-containing gas into the first section of reactor to perform butene oxidative dehydrogenation;
d) and (3) introducing the effluent of the hot effluent outlet of the heat exchanger at the outlet of each section of reactor, the butene used in the next section and the oxygen-containing gas which are respectively metered into the reactor in the next section till the reactor in the last section to obtain the butadiene product.
7. The method of claim 6, wherein the molar ratio of butene, oxygen-containing gas as oxygen and water vapor at the inlet of each reactor is 1: 0.3-0.8: 10-30, preferably 1: 0.4-0.6: 15-25;
the reaction conditions in each stage of the reactor independently include: the pressure is 0 to 1000kPa, preferably 0 to 500 kPa; the temperature is 250-600 ℃, preferably 300-500 ℃.
8. The method according to claim 6 or 7, wherein the condensate is an evaporative condensate and/or boiler circulating water; and/or the temperature of the condensate is 20-200 ℃.
9. The method according to any one of claims 6 to 8, wherein the oxygen-containing gas is selected from air and/or pure oxygen.
10. The process according to any one of claims 6 to 9, wherein the water vapor is introduced into the heat exchanger at the outlet of each stage of the reactor in sequence or in reverse order.
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