WO2022214069A1 - 一种撤热管组、反应温度控制方法和不饱和腈的制造方法 - Google Patents

一种撤热管组、反应温度控制方法和不饱和腈的制造方法 Download PDF

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Publication number
WO2022214069A1
WO2022214069A1 PCT/CN2022/085770 CN2022085770W WO2022214069A1 WO 2022214069 A1 WO2022214069 A1 WO 2022214069A1 CN 2022085770 W CN2022085770 W CN 2022085770W WO 2022214069 A1 WO2022214069 A1 WO 2022214069A1
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Prior art keywords
heat
pipes
pipe
heat withdrawal
section
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PCT/CN2022/085770
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English (en)
French (fr)
Inventor
赵乐
吴粮华
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Priority claimed from CN202110384148.XA external-priority patent/CN115337872B/zh
Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司上海石油化工研究院 filed Critical 中国石油化工股份有限公司
Priority to EP22784135.0A priority Critical patent/EP4321245A1/en
Priority to JP2023561320A priority patent/JP2024513885A/ja
Priority to US18/553,224 priority patent/US20240181418A1/en
Priority to KR1020237037361A priority patent/KR20230165912A/ko
Publication of WO2022214069A1 publication Critical patent/WO2022214069A1/zh

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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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/18—Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836—Heating and cooling the reactor
    • 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
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
    • C07C255/07—Mononitriles
    • C07C255/08—Acrylonitrile; Methacrylonitrile
    • 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
    • F28D13/00—Heat-exchange apparatus using a fluidised bed
    • 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
    • B01J2208/00115—Controlling the temperature by indirect heat exchange with heat exchange elements inside the bed of solid particles
    • B01J2208/00132—Tubes
    • 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
    • F28D1/00—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators
    • F28D1/02—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid
    • F28D1/04—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits
    • F28D1/047—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being bent, e.g. in a serpentine or zig-zag
    • F28D1/0477—Heat-exchange apparatus having stationary conduit assemblies for one heat-exchange medium only, the media being in contact with different sides of the conduit wall, in which the other heat-exchange medium is a large body of fluid, e.g. domestic or motor car radiators with heat-exchange conduits immersed in the body of fluid with tubular conduits the conduits being bent, e.g. in a serpentine or zig-zag the conduits being bent in a serpentine or zig-zag

Definitions

  • the present invention relates to a heat removal pipe group, which is particularly suitable for being arranged in a fluidized bed reactor.
  • the present invention further relates to a reaction temperature control method and a method for producing an unsaturated nitrile using the heat removal pipe group.
  • Acrylonitrile is an important chemical raw material for petrochemical industry.
  • Ammoxidation of propylene is widely used in countries all over the world to produce acrylonitrile by one-step ammoxidation, that is, under the action of a fluidized bed ammoxidation catalyst, under a certain reaction temperature and pressure, ammoxidation of propylene produces acrylonitrile, and at the same time, acetonitrile, hydrocyanic acid, etc. are by-products. There will also be the formation of deep oxidation products of CO and CO 2 . The reaction is strongly exothermic, and a large amount of heat is generated during the reaction.
  • Typical internal components of acrylonitrile fluidized bed reactor include propylene ammonia distributor, air distribution plate, heat extraction pipe (also known as cooling coil) and cyclone separator, wherein the heat extraction pipe and the feed leg of the cyclone separator serve as the fluidized bed
  • the vertical members are located in the catalyst bed.
  • the heat removal pipe can remove the large amount of reaction heat from the reaction system in time and maintain the reaction temperature in a stable state, while the cyclone separator captures the catalyst entrained with the gas moving upward, and returns the catalyst to the catalyst bed through the feed leg layer to reduce catalyst run-off.
  • Fig. 1 shows an acrylonitrile fluidized bed reactor, and its main internal components include: oxygen-containing gas distribution plate, acryl ammonia distributor, heat extraction pipe, and cyclone separator.
  • oxygen-containing gas distribution plate 85% or more of the total heat removal pipes are in working state, that is, the cooling pipes relative to the reaction temperature pass through them.
  • the heat removal medium can maintain the stability of the reaction temperature through the heat exchange of the heat removal medium.
  • the purpose of fine-tuning the temperature of the reactor is often achieved by switching the heat removal pipe during the reaction process.
  • the inventors of the present invention found that, in the fluidized bed reactor, in order to change the reaction temperature, it is necessary to switch between heat removal pipes with different heat removal amounts. Even when switching between different heat removal tubes with the smallest difference in heat removal, the variation of the reaction temperature is more than 3°C, which leads to the problem of poor control accuracy of the reaction temperature. Although it is possible to increase or decrease the feed amount of the raw material gas, that is, to increase or decrease the reaction heat, so that the exothermic heat of the reaction is equivalent to the heat removal capacity of the heat removal tube in the working state, but the change of the feed amount of the raw material gas is about ⁇ 1%.
  • the inventors of the present invention also found that, in the fluidized bed reactor, parameters such as the feed amount of the raw material gas, reaction temperature, reaction pressure and steam drum pressure when the device is running at full load are all known.
  • the heat removal capacity of the heat removal pipe in the device can also be estimated. Therefore, by finely adjusting the difference in heat transfer area between different heat removal pipes, the fine adjustment of the difference in heat removal between different heat removal pipes can be achieved.
  • the present invention has been completed based on this finding.
  • the present invention relates to the following aspects:
  • a heat-extraction pipe group (especially a heat-extraction pipe group), characterized in that the heat-extraction pipe group is configured to be arranged in the heat-extraction section of the fluidized-bed reactor, and the heat-extraction section is arranged in the In the fluidized bed layer of the fluidized bed reactor, the heat removal pipe group includes:
  • the first heat withdrawal pipe includes n1 (2 ⁇ n1 ⁇ 30, preferably 2 ⁇ n1 ⁇ 20, more preferably 2 ⁇ n1 ⁇ 10) parallel to the fluidized bed reactor
  • the straight pipes a and n1-1 extending in the direction of the central axis are used for connecting two adjacent straight pipes a in series and in fluid communication;
  • At least one second heat withdrawal pipe the second heat withdrawal pipe includes n2 (2 ⁇ n2 ⁇ 30, preferably 2 ⁇ n2 ⁇ 20, more preferably 2 ⁇ n2 ⁇ 10) parallel to the fluidized bed reactor
  • the straight pipes b and n2-1 extending in the direction of the central axis are used to connect two adjacent straight pipes b in series and fluidly communicate with each other,
  • any position of the heat withdrawal section (set the length of the heat withdrawal section along the central axis of the fluidized bed reactor to be L (unit is m), preferably at the length of the heat withdrawal section In the whole area of L, more preferably in the area of 49%L above and below the center point of the reaction heat removal section, more preferably in the area above 45%L and below the center point of the reaction heat removal section 38%L, more preferably In the area of 40% L above the center point of the reaction heat withdrawal section and below 8% L), a cross-section is obtained along the direction perpendicular to the central axis of the fluidized-bed reactor to obtain a cross-section,
  • the number of all straight pipes a of the first heat withdrawal pipes (when there are multiple ones, the multiple first heat withdrawal pipes combined together) is the same as the number of the second heat withdrawal pipes (when there are multiple ones, it is The number of all the straight pipes b of the plurality of second heat withdrawal pipes together) is the same, and all the second heat withdrawal pipes (when there are multiple second heat withdrawal pipes together) are all of the same number of straight pipes b.
  • the total perimeter Lb of the outer contour of the straight pipe b on the cross section is where all the straight pipes a of the first heat withdrawal pipe (if there are multiple ones, the multiple first heat withdrawal pipes are combined together) are located.
  • the ratio between the total perimeters La of the outer contours on the transverse plane is 1.25-2 (preferably 1.3-2 or 1.5-2).
  • the heat removal pipe group according to any one of the foregoing or later, characterized in that more than 50% (preferably 60% or more, more preferably 70% or more) of all the straight pipes a of the first heat removal pipe
  • the straight pipe a is within the range of the central portion of the cross section of the heat withdrawal section of the fluidized bed reactor, and less than 50% (preferably 40% or less, or more) of all the straight pipes b of the second heat withdrawal pipe.
  • the straight pipe b of 30% or less is within the range of the central portion of the cross-section, and/or, if the radius of the cross-section is R (unit is m), the range of the central portion is the distance from the The center of the cross section is in the range of 3/4R (preferably in the range of 2/3R, more preferably in the range of 1/2R, still more preferably in the range of 1/3R).
  • the heat removal pipe group according to any one of the foregoing or later, characterized in that the ratio of the outer diameter (unit is mm) of the straight pipe a to the outer diameter (unit is mm) of the straight pipe b is: 1-1.8, preferably 1-1.5; or, the ratio of the outer diameter (unit is mm) of the straight pipe b to the outer diameter (unit is mm) of the straight pipe a is 1-1.8, preferably 1- 1.5.
  • the heat removal pipe set according to any one of the preceding or following aspects characterized in that the outer diameters of the straight pipes a are independently 80-180 mm, preferably 90-170 mm, and the lengths of the straight pipes a are independent of each other.
  • the ground is 4-13m, preferably 5-12.0m
  • the distance between two adjacent straight pipes a is 100-700mm, preferably 150-500mm, and/or, the outer diameters of the straight pipes b are independently 80-180mm, preferably 90-170mm
  • the lengths of the straight pipes b are independently 4-13m, preferably 5-12.0m
  • the distance between two adjacent straight pipes b is 100-700mm, preferably 150- 500mm
  • the total perimeter of the outer contour of one of the first heat withdrawal pipes is 0.5-17m, preferably 2.5-11.3m
  • the total circumference of the outer contour of one of the second heat withdrawal pipes is 0.5-17m, preferably 2.5-11.3m.
  • the heat removal pipe group according to any one of the preceding or following aspects, wherein the length L of the heat removal section is 4-12.5m, preferably 5.5-11.5m, and/or the radius R is 5 -29m, preferably 7-20m, and/or, the number of the first heat withdrawal pipes is 1-4 or 1, and/or the second heat withdrawal pipes are 1-4 or 1 in number, And/or, the heat removal pipe group includes at least one pair (preferably 1-20 pairs, more preferably 2-10 pairs or 2-5 pairs) heat removal pipes, and each pair of the heat removal pipes is composed of the at least 1 first heat removal pipe.
  • the heat extraction pipe and the at least one second heat extraction pipe are formed.
  • the heat extraction pipe group according to any one of the preceding or following aspects, characterized in that, under the same operating conditions of the fluidized bed reactor, the first heat extraction pipes (when there are multiple ones, there are multiple ones of the The adjustment range of the first heat withdrawal pipe (together) to the reaction temperature of the fluidized bed reactor is the same as that of the second heat withdrawal pipe (when there are multiple ones, a plurality of the second heat withdrawal pipes are combined together)
  • the difference (absolute value) of the adjustment range of the reaction temperature of the fluidized-bed reactor is 0.5-3°C (preferably 1-2°C), and/or, when there are more than one, at least 2 (preferably all) of all
  • the cooling water inlets of the first heat withdrawal pipes are combined into a cooling water inlet header in the heat withdrawal section, and/or, when there are multiple, at least 2 (preferably all) cooling water of the first heat withdrawal pipes
  • the water outlets are merged into one cooling water outlet header in the heat removal section, and/or, when there are multiple, at least 2 (preferably all) cooling
  • a fluidized bed reactor characterized in that it comprises a head, a dilute phase zone, a heat withdrawal section, a pre-reaction section and a cone in sequence from top to bottom, wherein the foregoing or the latter is arranged in the heat withdrawal section
  • the heat removal pipe group described in any one of the above-mentioned aspects.
  • the temperature control method for a fluidized bed reactor characterized in that, during the reaction process, the first heat withdrawal pipes (when there are multiple, multiple The first heat withdrawal pipes are combined together) to the second heat withdrawal pipes (when there are multiple ones, a plurality of the second heat withdrawal pipes are combined together), so that the reaction temperature of the fluidized bed reactor can be adjusted Raise or lower by 0.5-3°C (preferably 1-2°C).
  • a method for producing unsaturated nitrile comprising ammoxidation reaction of olefin (such as propylene) to generate unsaturated nitrile (such as acrylonitrile) in the fluidized bed reactor according to any one of the foregoing or the following aspects step.
  • olefin such as propylene
  • unsaturated nitrile such as acrylonitrile
  • a method for producing unsaturated nitrile comprising the step of ammoxidizing olefin (such as propylene) in a fluidized-bed reactor to generate unsaturated nitrile (such as acrylonitrile), wherein according to any of the foregoing or later
  • the temperature control method of the aspect controls the temperature of the fluidized bed reactor.
  • Figure 1 is a schematic front view of a prior art fluidized bed reactor.
  • Fig. 2 is a schematic top view of a prior art fluidized bed reaction heat removal tube group.
  • FIG. 3 is a schematic diagram of the heat removal pipe group of the present invention.
  • FIG. 4 and FIG. 5 are schematic diagrams of the heat evacuation tube header of the present invention.
  • fine adjustment of the reaction temperature can be achieved when the first heat removal pipe and the second heat removal pipe are linked and switched in a paired manner through fine adjustment of the difference in heat removal between different heat removal pipes.
  • the so-called “substantially” refers to allowing a deviation that is acceptable or considered reasonable for those skilled in the art, such as deviation within ⁇ 10%, within ⁇ 5%, within ⁇ 1%, Within ⁇ 0.5% or within ⁇ 0.1%.
  • any two or more embodiments of the present invention can be combined arbitrarily, and the technical solutions formed thereby belong to a part of the original disclosure content of this specification, and also fall within the protection scope of the present invention.
  • exhaust tubes and “exhaust tubes” can be used to remove excess heat from a reactor undergoing an exothermic reaction (or certain exothermic stages of a reaction) to maintain the reaction within a certain temperature range.
  • a reactor in particular a fluidized bed reactor, more particularly a fluidized bed reactor for the manufacture of acrylonitrile.
  • the heat withdrawal tube group is configured to be arranged in the heat withdrawal section of the fluidized bed reactor.
  • the heat withdrawal pipe is also configured to be arranged in the heat withdrawal section of the fluidized bed reactor.
  • the straight pipes of the heat removal pipe are basically located in the dense phase zone of the fluidized bed reactor, so as to remove the reaction heat from the system in time and maintain the stable operation of the system.
  • the so-called "heat withdrawal section” refers to the area in the fluidized bed reactor where the heat withdrawal pipe is arranged, and more particularly refers to the straight pipe of the heat withdrawal pipe in the fluidized bed reactor.
  • the region in the fluidized bed reactor more particularly, refers to the region in the dense phase zone of the fluidized bed reactor where the straight pipe of the heat withdrawal pipe is arranged.
  • the heat-extraction pipe group in the heat-extraction section is generally arranged in the manner shown in FIG. 2 , that is, the heat-extraction pipes are arranged in a straight line.
  • the heat removal section of the fluidized bed reactor also includes other internal components such as the feed legs of the cyclone separator 9 .
  • the heat removal pipe includes a cooling water inlet, a straight pipe and a cooling water outlet, and connecting pipes that fluidly communicate these lines.
  • each heat removal pipe includes a cooling water inlet 3 , a cooling water outlet 4 , a plurality of straight pipes and a connecting pipe for connecting any two adjacent straight pipes in series and in fluid communication.
  • the heat withdrawal pipe group includes at least one first heat withdrawal pipe.
  • the first heat withdrawal pipe includes n1 (2 ⁇ n1 ⁇ 30, preferably 2 ⁇ n1 ⁇ 20, more preferably 2 ⁇ n1 ⁇ 10) extending parallel to the central axis direction of the fluidized bed reactor
  • the straight pipes a and n1-1 are used for connecting two adjacent straight pipes a in series and in fluid communication.
  • the number of the first heat withdrawal pipes is 1-4 or 1.
  • the heat withdrawal pipe group includes at least one second heat withdrawal pipe.
  • the second heat withdrawal pipe includes n2 (2 ⁇ n2 ⁇ 30, preferably 2 ⁇ n2 ⁇ 20, more preferably 2 ⁇ n2 ⁇ 10) extending parallel to the central axis of the fluidized bed reactor
  • the straight pipes b and n2-1 are used for connecting two adjacent straight pipes b in series and in fluid communication.
  • the number of the second heat withdrawal pipes is 1-4 or 1.
  • the entire length L of the heat removal section is The cross-section of the heat withdrawal section is obtained when the area is cross-sectioned along the direction perpendicular to the central axis of the fluidized-bed reactor.
  • the so-called cross section of the heat removal section refers to the cross section of the inner contour of the fluidized bed reactor at the heat removal section.
  • the region is preferably within a region of 49%L above and below the center point of the reaction heat removal section, more preferably within a region above 45%L and below the center point of the reaction heat removal section by 38%L, and more preferably within In the area above 40%L and below 8%L of the center point of the reaction heat removal section.
  • the length L of the heat removal section is 4-12.5m, preferably 5.5-11.5m.
  • the number of all straight pipes a of the first heat withdrawal pipes (when there are multiple ones, the plurality of first heat withdrawal pipes combined together) is the same as the number of the second heat withdrawal pipes (in the When there are more than one, the number of all the straight pipes b is the same as the number of the second heat withdrawal pipes combined).
  • the total circumference of the outer contour of all the straight pipes b of the second heat withdrawal pipes (when there are multiple second heat withdrawal pipes together) on the cross-section plane The difference between the length Lb and the total perimeter La of the outer contour on the cross section of all straight pipes a of the first heat withdrawal pipes (if there are multiple first heat withdrawal pipes together)
  • the ratio is 1.25-2 (preferably 1.3-2 or 1.5-2).
  • the heat conduction capacity of the central area where the heat extraction pipe a is located is higher than that of the outer periphery where the heat extraction pipe b is located.
  • the outer contour perimeter of a heat removal pipe is the sum of the outer contour perimeters of n heat removal straight pipes or the outer contour perimeter is directly represented by n*3.14*D (D is the average outer diameter of the heat removal straight pipes), usually the number of straight pipes The more, the longer the perimeter of the outer contour, and the stronger the heat removal capacity during the operation of the device. Therefore, for the heat removal pipe group,
  • by setting different pipe outer diameters if
  • the ratio of the outer diameter (unit is mm) of the straight pipe a to the outer diameter (unit is mm) of the straight pipe b is 1-1.8, preferably 1-1.5.
  • the ratio of the outer diameter (unit is mm) of the straight pipe b to the outer diameter (unit is mm) of the straight pipe a is 1-1.8, preferably 1-1.5.
  • the outer diameters of the straight pipes a are each independently 80-180 mm, preferably 90-170 mm, and the lengths of the straight pipes a are each independently 4-13 m, preferably 5-12.0 m, And the distance between two adjacent straight pipes a is 100-700mm, preferably 150-500mm.
  • the outer diameters of the straight pipes b are each independently 80-180 mm, preferably 90-170 mm, and the lengths of the straight pipes b are each independently 4-13 m, preferably 5-12.0 m, And the distance between two adjacent straight pipes b is 100-700mm, preferably 150-500mm.
  • the total perimeter of the outer contour of one of the first heat withdrawal pipes is 0.5-17 m, preferably 2.5-11.3 m.
  • the total circumference of the outer contour of one of the second heat extraction pipes is 0.5-17 m, preferably 2.5-11.3 m.
  • the heat-extraction pipe group comprises at least one pair (preferably 1-20 pairs, more preferably 2-10 pairs or 2-5 pairs) of heat-extraction pipes, and each pair of the heat-extraction pipes is composed of the at least one pair of heat-extraction pipes.
  • a first heat extraction pipe and the at least one second heat extraction pipe are formed.
  • the heat-extraction pipe group comprises at least one (preferably 1-20, more preferably 2-10 or 2-5) heat-extraction pipe pairs, each pair of heat-extraction pipes It consists of the at least one first heat extraction pipe and the at least one second heat extraction pipe.
  • first heat withdrawal pipe and the second heat withdrawal pipe refer to the first heat withdrawal pipe and the second heat withdrawal pipe in the same heat withdrawal pipe pair.
  • the present invention is not intended to be limited to different heat withdrawal pipe pairs, the relationship between the first heat withdrawal pipe of one heat withdrawal pipe pair and the second heat withdrawal pipe of the other heat withdrawal pipe pair, or the first heat withdrawal pipe of one heat withdrawal pipe pair.
  • the at least one first heat evacuation pipe and the at least one second heat evacuation pipe do not work at the same time, but switch operations according to the needs of the production operation, that is, the at least one first heat evacuation pipe is in the process of evacuation.
  • the at least one second heat withdrawal pipe is in an idle state, and the first heat withdrawal pipe and the second heat withdrawal pipe are cut off by closing the valve between the external cooling coil of the reactor and the first heat withdrawal pipe.
  • the circulation of the coolant in the first heat withdrawal pipe makes the first heat withdrawal pipe in the heat withdrawal operation idle, and at the same time, the valve between the external cooling coil of the reactor and the second heat withdrawal pipe is opened, so that the coolant flows in the second heat withdrawal pipe.
  • the second heat withdrawal pipe in the idle state is in the heat withdrawal operation state; on the contrary, the first heat withdrawal pipe and the second heat withdrawal pipe can also be switched in reverse operation.
  • the valve between the first heat withdrawal pipe makes the fluid flow of the coolant in the first heat withdrawal pipe, so that the first heat withdrawal pipe in the idle state is in the heat withdrawal operation, and at the same time closes the valve between the external cooling coil of the reactor and the second heat withdrawal pipe to cut off the cooling
  • the fluid flows of the agent in the second heat extraction pipe, so that the second heat extraction pipe in the heat extraction operation is in an idle state.
  • the at least one first heat extraction pipe and the at least one second heat extraction pipe are the heat extraction pipes in the same heat extraction pipe pair.
  • the first heat withdrawal pipe (if there are multiple ones, the plurality of first heat withdrawal pipes are combined together) to the fluidized bed reactor
  • the difference between the adjustment range of the reaction temperature of the fluidized bed reactor and the adjustment range of the reaction temperature of the fluidized bed reactor absolute value
  • the present invention can realize precise control of the reaction temperature when the heat removal pipes are switched within the same heat removal pipe pair.
  • the straight pipe a in the cross-section of the heat removal section, more than 50% (preferably more than 60%, more preferably more than 70%) of all the straight pipes a of the first heat removal pipe
  • the straight pipe a is within the range of the central portion of the cross section of the heat withdrawal section of the fluidized bed reactor, and less than 50% (preferably 40% or less, or more) of all the straight pipes b of the second heat withdrawal pipe. It is preferable that the straight pipe b of 30% or less) is within the range of the central portion of the cross section.
  • first heat removal pipe 10 has 8 straight pipes
  • more than 5 straight pipes are in the range of the central portion of the cross section
  • more than 4 straight pipes are in the range of the central portion of the cross section
  • the second heat removal pipe 20 has 6 straight pipes
  • 2 or less straight pipes are in the range of the central portion of the cross section
  • the second heat removal pipe 20 has 5 straight pipes
  • 2 The following straight pipes are in the range of the central part of the cross section.
  • the central part of the cross section refers to the The range within a certain distance from the center of the circular cross section (that is, the range within the dotted line in Figure 3), and the peripheral area of the cross section refers to the area outside the central part (i.e. the dotted line in Figure 3 to the reactor extent of wall 1).
  • the central portion of the cross section refers to a circular area within 3/4R of the center of the cross section, preferably a circular area within 2/3R of the center of the cross section, more preferably The circular area within 1/2R from the center of the cross section is still more preferably a circular area within 1/3R from the center of the cross section.
  • the radius R is 5-29 m, preferably 7-20 m.
  • the cooling water inlets of at least 2 (preferably all) of the first heat withdrawal pipes are combined into a cooling water inlet header in the heat withdrawal section.
  • a plurality of the heat removal pipes (called branch pipes) share one cooling water inlet.
  • the cooling water inlet header is in fluid communication with an external cooling water supply source through the wall of the fluidized bed reactor, thereby supplying cooling water to each branch pipe through the cooling water inlet header.
  • the cooling water outlets of at least 2 (preferably all) of the second heat withdrawal pipes are combined into a cooling water outlet header in the heat withdrawal section.
  • a plurality of the heat removal pipes (called branch pipes) share one cooling water outlet.
  • the cooling water outlet header passes through the wall of the fluidized bed reactor and is in fluid communication with the external cooling water receiving device, so that the cooling water outlet header transfers heat from each branch pipe to the outside world.
  • the subsequent cooling water generally also contains steam).
  • the cooling water inlets of at least 2 (preferably all) of the second heat withdrawal pipes are combined into a cooling water inlet header in the heat withdrawal section.
  • a plurality of the heat removal pipes (called branch pipes) share one cooling water inlet.
  • the cooling water inlet header is in fluid communication with an external cooling water supply source through the wall of the fluidized bed reactor, thereby supplying cooling water to each branch pipe through the cooling water inlet header.
  • the cooling water outlets of at least 2 (preferably all) of the second heat withdrawal pipes are combined into a cooling water outlet header in the heat withdrawal section.
  • a plurality of the heat removal pipes (called branch pipes) share one cooling water outlet.
  • the cooling water outlet header passes through the wall of the fluidized bed reactor and is in fluid communication with the external cooling water receiving device, so that the cooling water outlet header transfers heat from each branch pipe to the outside world.
  • the subsequent cooling water generally also contains steam).
  • FIG. 4 and FIG. 5 are schematic diagrams of the arrangement of the heat evacuation pipe header of the present invention. As can be seen from the figure, the cooling water outlet/inlet of multiple heat removal pipes are aggregated into one header.
  • the cross-sectional area of the header (such as the cooling water inlet header or the cooling water outlet header) corresponds to the plurality of branch pipes (generally the plurality of The ratio of the sum of the cross-sectional areas of the cooling water inlet or cooling water outlet of the branch pipes is 0.5-1, preferably 0.55-0.95, more preferably 0.6-0.9.
  • the heat withdrawal pipe group includes: at least one first heat withdrawal pipe, and the first heat withdrawal pipe includes n1 (2 ⁇ n1 ⁇ 30, preferably 2 ⁇ n1 ⁇ 20, more preferably 2 ⁇ n1 ⁇ 10) straight pipes a extending parallel to the direction of the central axis of the fluidized bed reactor and n1-1 connecting pipes for connecting the n1 straight pipes in series and in fluid communication; and at least 1
  • the second heat withdrawal pipe, the second heat withdrawal pipe includes n2 (2 ⁇ n1 ⁇ 30, preferably 2 ⁇ n1 ⁇ 20, more preferably 2 ⁇ n1 ⁇ 10) parallel to the central axis direction of the fluidized bed reactor
  • the extended straight pipes b and n2-1 are connecting pipe pieces for making the n2 straight pipes in series and in fluid communication, wherein at any position
  • the total straight pipe b of the second heat withdrawal pipe is less than 50% (preferably 40% or less, more preferably 30% or less)
  • the straight pipe b is within the range of the central portion of the cross section, and wherein, the total perimeter Lb of the outer contour of all the straight pipes b of the second heat withdrawal pipe is the same as the outer contour of all the straight pipes a of the first heat withdrawal pipe
  • the ratio between the total perimeters La is 1.5-2.
  • a fluidized bed reactor which sequentially includes a head, a dilute phase zone, a heat removal section, a pre-reaction section and a cone from top to bottom.
  • the heat-extraction pipe group described in the foregoing description of the present specification is arranged in the heat-extraction section.
  • the present invention also relates to a temperature control method for a fluidized bed reactor.
  • the fluidized-bed reactor is preferably the fluidized-bed reactor described earlier in this specification.
  • the temperature control method includes, during the reaction, switching the first heat withdrawal pipe (when there are multiple first heat withdrawal pipes together) to the first heat withdrawal pipe
  • the second heat withdrawal pipe if there are multiple ones, a plurality of the second heat withdrawal pipes are combined together, so as to increase or decrease the reaction temperature of the fluidized bed reactor by 0.5-3°C (preferably 1-2°C). °C).
  • the present invention also relates to a method for producing unsaturated nitrile, comprising the step of ammoxidizing olefin (such as propylene) in a fluidized bed reactor to generate unsaturated nitrile (such as acrylonitrile).
  • the fluidized-bed reactor can be temperature-controlled according to the temperature control method described earlier in this specification, so as to maintain the reaction temperature of the fluidized-bed reactor substantially constant, so as to realize fine adjustment of the reaction temperature.
  • the present invention also relates to a method for producing unsaturated nitrile, comprising the step of ammoxidizing olefin (such as propylene) in a fluidized bed reactor to generate unsaturated nitrile (such as acrylonitrile).
  • the fluidized-bed reactor is preferably the fluidized-bed reactor described earlier in this specification.
  • the ammoxidation reaction can be carried out in any manner and any method conventionally known in the art, such information is known to those skilled in the art and will not be repeated herein.
  • the operating conditions of the ammoxidation reaction for example, the molar ratio of propylene/ammonia/air (in terms of molecular oxygen) is generally 1:1.1-1.3:1.8-2.0, and the reaction temperature is generally 420 -440°C, the reaction pressure (gauge pressure) is generally 0.03-0.14MPa, and the weight hourly space velocity of the catalyst is generally 0.04-0.15h -1 .
  • Cc 3 out the number of moles of carbon (mol) contained in C 3 in the inlet gas of the reactor.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the ratio of the outer diameter of the branch pipe a to the outer diameter of the branch pipe b is 0.53, and the ratio of the total circumference of the outer contour of all the straight pipes constituting the second heat extraction pipe to the total circumference of the outer contour of the straight pipes constituting the first heat withdrawing pipe is 1.89.
  • reaction temperature Under the conditions of propylene feed rate of 11800NM 3 /h, reaction temperature of 430°C, reaction pressure of 0.04Mpa, and propylene:ammonia:air ratio of 1:1.2:9.6, through the air between the first heat extraction pipe and the second heat extraction pipe
  • the reactor temperature can be finely adjusted in 2.0°C ramp-up or ramp-down.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the ratio of the outer diameter of the branch pipe a to the outer diameter of the branch pipe b is 0.66, and the ratio of the total circumference of the outer contour of all the straight pipes constituting the second heat extraction pipe to the total circumference of the outer contour of the straight pipes constituting the first heat withdrawing pipe is 1.52.
  • reaction temperature Under the conditions of propylene feed rate of 11800NM 3 /h, reaction temperature of 430°C, reaction pressure of 0.04Mpa, and propylene:ammonia:air ratio of 1:1.2:9.6, through the air between the first heat extraction pipe and the second heat extraction pipe
  • the reactor temperature can be finely adjusted in 1.3°C ramp-up or ramp-down.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the other heat extraction pipe is the second heat extraction pipe composed of 8 straight pipes b in series, and the 6 straight pipes b of the second heat extraction pipe are located in the cross section of the heat extraction section of the reactor.
  • the ratio of the outer diameter of the branch pipe b to the outer diameter of the branch pipe a is 1.54, and the ratio of the total circumference of the outer contour of all straight pipes constituting the second heat extraction pipe to the total circumference of the outer contour of the straight pipes constituting the first heat withdrawing pipe is 1.54.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the ratio of the outer diameter of the branch pipe b to the branch pipe a is 1.35, and the total perimeter of the outer contour of all the straight pipes constituting the second heat withdrawal pipe and the total perimeter of the outer contour of the straight pipes constituting the first heat withdrawal pipe are summed.
  • the ratio is 1.35.
  • the temperature of the reactor can be finely adjusted with a heating or cooling range of 1.6°C by switching between the first heat removal pipe and the second heat removal pipe of the heat removal pipe group.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the first heat-extraction pipe has 14 straight pipes a in series.
  • the other heat removal pipe is a second heat removal pipe composed of 10 straight pipes b in series and 10 straight pipes b in series.
  • the 15 straight pipes b are located outside the range of 2/3R from the center of the circle in the cross section of the heat withdrawal section of the reactor.
  • the ratio of the outer diameter of the branch pipe b to the outer diameter of the branch pipe a is 1.69, and the ratio of the total circumference of the outer contour of all the straight pipes constituting the second heat extraction pipe to the total circumference of the outer contour of the straight pipes constituting the first heat withdrawing pipe is 1.69.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the other heat removal pipe is composed of a second heat removal pipe composed of 8 straight pipes b in series and 8 straight pipes b in series; And the ratio of the total perimeter of the outer contour of all the straight pipes constituting the second heat withdrawal pipe to the total circumference of the outer contour of the straight pipes constituting the first heat withdrawal pipe is 1.35.
  • the outer diameter of the inlet header of the heat extraction pipe b is 140mm, and the outer diameter of the outlet header of the heat extraction pipe b is 150mm.
  • the ratio of the sum of the cross-sectional areas is 0.78; the outer diameter of the inlet header of the heat extraction pipe a is 120mm, the outer diameter of the outlet header of the heat extraction pipe a is 120mm, the ratio of the cross-sectional area of the inlet header to the cross-sectional area of the heat extraction branch pipe is 0.90, and the outlet header is 0.90.
  • the ratio of the sum of the cross-sectional area of the pipe to the cross-sectional area of the heat-extracting branch pipe is 0.90.
  • the temperature of the reactor can be finely adjusted with a heating or cooling range of 1.3°C by switching between the first heat removal pipe and the second heat removal pipe of the heat removal pipe group.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the diameter of the fluidized bed reactor is 9 meters, and it is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • the ratio of the outer diameter of the branch pipe b to the outer diameter of the branch pipe a is 2.2
  • the ratio of the total perimeter of the outer contour of all straight pipes b constituting the second heat extraction pipe to the total perimeter of the outer contour of the straight pipes a constituting the first heat extraction pipe is 2.20.

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Abstract

一种撤热管组、使用该撤热管组的反应温度控制方法和不饱和腈的制造方法。该撤热管组包括至少1个第一撤热管（10）和至少1个第二撤热管（20），第一撤热管（10）的全部直管（5）a的数量与第二撤热管（20）的全部直管（5）b的数量相同，并且第二撤热管（20）的全部直管（5）b在横切面上的外轮廓总周长Lb与第一撤热管（10）的全部直管（5）a在横切面上的外轮廓总周长La之间的比值为1.25-2。第一撤热管（10）和第二撤热管（20）按照成对方式联动切换，精细调节反应温度。

Description

一种撤热管组、反应温度控制方法和不饱和腈的制造方法 技术领域
本发明涉及一种撤热管组，所述撤热管组特别适合设置在流化床反应器中。本发明进一步涉及使用所述撤热管组的反应温度控制方法和不饱和腈的制造方法。
背景技术
丙烯腈是石油化工的重要化工原料。世界各国普遍采用丙烯氨氧化一步法生产丙烯腈，即在流化床氨氧化催化剂作用下，在一定的反应温度和压力下，丙烯氨氧化生成丙烯腈，同时副产乙腈、氢氰酸等，也会有CO、CO 2深度氧化产物的生成。该反应为强放热反应，反应过程中伴随着大量的热量产生。
典型的丙烯腈流化床反应器内构件包括丙烯氨分布器、空气分布板、撤热管(也称为冷却盘管)及旋风分离器，其中撤热管及旋风分离器的料腿作为流化床的垂直构件位于催化剂床层中。撤热管可以将大量产生的反应热及时移出反应系统，并将反应温度维持在一个稳定的状态，而旋风分离器捕获随气体向上运动时所夹带的催化剂，并将催化剂通过料腿返送回催化剂床层，以减少催化剂跑损。
图1示出一种丙烯腈流化床反应器，其主要内构件包括：含氧气体分布板、丙烯氨分布器、撤热管、旋风分离器。在如图1所示的现有技术的丙烯腈反应器中，需总撤热管的85％甚至更多的撤热管都处于工作状态，即这些撤热管内均通有相对反应温度来说的冷的撤热介质，通过撤热介质的热交换，才能维持反应温度的稳定。此外，反应过程中往往通过切换撤热管来达到微调反应器温度的目的。
发明内容
本发明的发明人发现，在流化床反应器中，为了改变反应温度， 需要在撤热量不同的撤热管之间进行切换。即使是在撤热量差异最小的不同撤热管之间进行切换，反应温度的变化幅度也在3℃以上，由此引发反应温度的控制精度较差问题。虽然可以通过增加或减少原料气进料量，即增加或减少反应热，使得反应放热与处于工作状态下的撤热管撤热能力相当，但是导致原料气的进料量变化达±1％左右甚至更多，如此由于装置运行负荷的变化，增加了不稳定因素；或者可以通过调节蒸汽汽包压力的方式，但是汽包压力的波动会增加需蒸汽透平的设备如空压机、冰机等的操作难度。
本发明的发明人还发现，在流化床反应器中，装置满负荷运行时的原料气进料量、反应温度、反应压力以及汽包压力等参数都是已知的，对于流化床反应器中的撤热管的撤热能力也是可以预估的。因此，通过精细调节不同的撤热管之间的传热面积差异，就可以实现不同撤热管之间撤热量差异的精细调节。本发明基于该发现而完成。
具体而言，本发明涉及以下方面的内容：
1.一种撤热管组(特别是撤热水管组)，其特征在于，所述撤热管组被构造为设置在流化床反应器的撤热段内，所述撤热段设置于所述流化床反应器的流化床层内，所述撤热管组包括：
至少1个第一撤热管，所述第一撤热管包括n1(2<n1<30，优选为2<n1<20，更优选为2<n1<10)个平行于所述流化床反应器的中心轴线方向延伸的直管a和n1-1个用于使相邻两个直管a串联并流体连通的连接管件；和
至少1个第二撤热管，所述第二撤热管包括n2(2<n2<30，优选为2<n2<20，更优选为2<n2<10)个平行于所述流化床反应器的中心轴线方向延伸的直管b和n2-1个用于使相邻两个直管b串联并流体连通的连接管件，
在所述撤热段的任意位置处(设所述撤热段沿着所述流化床反应器中心轴线方向的长度为L(单位是m)，优选在所述撤热段的所述长度L的整个区域内，更优选在所述反应撤热段中心点上下49％L 的区域内，更优选在所述反应撤热段中心点以上45％L以下38％L的区域内，更优选在所述反应撤热段中心点以上40％L以下8％L的区域内)沿着垂直于所述流化床反应器中心轴线的方向横切而获得横切面，
其中，所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)的全部直管a的数量与所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)的全部直管b的数量相同，并且所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)的全部直管b在所述横切面上的外轮廓总周长Lb与所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)的全部直管a在所述横切面上的外轮廓总周长La之间的比值为1.25-2(优选为1.3-2或1.5-2)。
2.前述或后述任一方面所述的撤热管组，其特征在于，满足|n1-n2|<5(优选|n1-n2|<3)。
3.前述或后述任一方面所述的撤热管组，其特征在于，所述第一撤热管的全部直管a中的大于50％(优选60％以上、更优选为70％以上)的直管a在所述流化床反应器的所述撤热段的横切面的中心部分范围内，且所述第二撤热管的全部直管b中的小于50％(优选40％以下、更优选为30％以下)的直管b在所述横切面的中心部分范围内，和/或，设所述横切面的半径为R(单位是m)，则所述中心部分范围为距所述横切面的圆心3/4R范围内(优选为2/3R范围内，更优选为1/2R范围内，还更优选为1/3R范围内)。
4.前述或后述任一方面所述的撤热管组，其特征在于，所述直管a的外径(单位是mm)与所述直管b的外径(单位是mm)之比为1-1.8，优选为1-1.5；或者，所述直管b的外径(单位是mm)与所述直管a的外径(单位是mm)之比为1-1.8，优选为1-1.5。
5.前述或后述任一方面所述的撤热管组，其特征在于，所述直管a的外径各自独立地为80-180mm，优选90-170mm，所述直管a的长度各自独立地为4-13m，优选5-12.0m，并且相邻两个直管 a之间的间距为100-700mm，优选150-500mm，和/或，所述直管b的外径各自独立地为80-180mm，优选90-170mm，所述直管b的长度各自独立地为4-13m，优选5-12.0m，并且相邻两个直管b之间的间距为100-700mm，优选150-500mm，和/或，1个所述第一撤热管的外轮廓总周长为0.5-17m，优选2.5-11.3m，和/或，1个所述第二撤热管的外轮廓总周长为0.5-17m，优选2.5-11.3m。
6.前述或后述任一方面所述的撤热管组，其特征在于，所述撤热段的长度L为4-12.5m，优选5.5-11.5m，和/或，所述半径R为5-29m，优选7-20m，和/或，所述第一撤热管的数量为1-4个或1个，和/或，所述第二撤热管的数量为1-4个或1个，和/或，所述撤热管组包括至少一对(优选1-20对，更优选2-10对或2-5对)撤热管，并且每对所述撤热管由所述至少1个第一撤热管和所述至少1个第二撤热管构成。
7.前述或后述任一方面所述的撤热管组，其特征在于，在相同的流化床反应器操作条件下，所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)对所述流化床反应器的反应温度的调节幅度与所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)对所述流化床反应器的反应温度的调节幅度的差异(绝对值)为0.5-3℃(优选1-2℃)，和/或，在存在多个时，至少2个(优选全部)所述第一撤热管的冷却水入口在所述撤热段内合并成一个冷却水入口集管，和/或，在存在多个时，至少2个(优选全部)所述第一撤热管的冷却水出口在所述撤热段内合并成一个冷却水出口集管，和/或，在存在多个时，至少2个(优选全部)所述第二撤热管的冷却水入口在所述撤热段内合并成一个冷却水入口集管，和/或，在存在多个时，至少2个(优选全部)所述第二撤热管的冷却水出口在所述撤热段内合并成一个冷却水出口集管。
8.一种流化床反应器，其特征在于，从顶到底顺次包括封头、稀相区、撤热段、预反应段和锥体，其中在所述撤热段中设置前述 或后述任一方面所述的撤热管组。
9.前述或后述任一方面所述的流化床反应器的温度控制方法，其特征在于，包括在反应过程中，将所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)切换至所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)，以将所述流化床反应器的反应温度升高或降低0.5-3℃(优选1-2℃)。
10.一种不饱和腈的制造方法，包括在前述或后述任一方面所述的流化床反应器中使烯烃(比如丙烯)发生氨氧化反应而生成不饱和腈(比如丙烯腈)的步骤。
11.一种不饱和腈的制造方法，包括在流化床反应器中使烯烃(比如丙烯)发生氨氧化反应而生成不饱和腈(比如丙烯腈)的步骤，其中按照前述或后述任一方面所述的温度控制方法对所述流化床反应器进行温度控制。
12.前述或后述任一方面所述的制造方法，其特征在于，丙烯/氨气/空气(以分子氧计)的摩尔比为1：1.1-1.3：1.8-2.0，反应温度为420-440℃，反应压力(表压)为0.03-0.14MPa，催化剂重时空速为0.04-0.15h -1。
附图说明
图1是现有技术的流化床反应器的正视示意图。
图2是现有技术的流化床反应撤热管组的俯视示意图。
图3是本发明的撤热管组示意图。
图4和图5是本发明的撤热管集管示意图。
附图标记说明：
1：流化床反应器器壁
2：流化床反应器的撤热管
3：撤热管的冷却水入口
4：撤热管的冷却水出口
5：撤热管的直管
6：撤热管的连接管件
7：含氧气体分布板
8：丙烯氨分布器
9：高效旋风分离器
10：第一撤热管
20：第二撤热管
技术效果
根据本发明，通过不同撤热管之间撤热量差异的精细调节，由此在第一撤热管和第二撤热管按照成对方式联动切换时，可以实现反应温度的精细调节。
具体实施方式
下面对本发明的具体实施方式进行详细说明，但是需要指出的是，本发明的保护范围并不受这些具体实施方式的限制，而是由附录的权利要求书来确定。
本说明书提到的所有出版物、专利申请、专利和其它参考文献全都引于此供参考。除非另有定义，本说明书所用的所有技术和科学术语都具有本领域技术人员常规理解的含义。在有冲突的情况下，以本说明书的定义为准。
当本说明书以词头“本领域技术人员公知”、“现有技术”或其类似用语来导出材料、物质、方法、步骤、装置或部件等时，该词头导出的对象涵盖本申请提出时本领域常规使用的那些，但也包括目前还不常用，却将变成本领域公认为适用于类似目的的那些。
在本说明书的上下文中，所谓“基本上”指的是允许存在对于本领域技术人员而言可以接受或认为合理的偏差，比如偏差在±10％以内、±5％以内、±1％以内、±0.5％以内或者±0.1％以内。
在没有明确指明的情况下，本说明书内所提到的所有百分数、 份数、比率等都是以重量为基准的，而且压力是表压。
在本说明书的上下文中，本发明的任何两个或多个实施方式都可以任意组合，由此而形成的技术方案属于本说明书原始公开内容的一部分，同时也落入本发明的保护范围。
根据本发明的一个实施方式，涉及一种撤热管组，特别是撤热水管组。根据本发明，“撤热管组”和“撤热管”可以用于从进行放热反应(或者反应的某些放热阶段)的反应器中移除多余热量，使反应维持在一定温度范围内。作为反应器的举例，特别是流化床反应器，更特别是丙烯腈制造用流化床反应器。
根据本发明的一个实施方式，所述撤热管组被构造为设置在流化床反应器的撤热段内。显然，所述撤热管同样被构造为设置在流化床反应器的撤热段内。具体而言，所述撤热管的直管基本上都位于所述流化床反应器的密相区，用于将反应热及时移出系统，维持系统的稳定运行。为此，在本说明书的上下文中，所谓“撤热段”，指的是所述流化床反应器中设置有撤热管的区域，更特别是指所述撤热管的直管在所述流化床反应器中所处的区域，更特别指的是所述流化床反应器的密相区中设置有所述撤热管的直管的区域。
根据现有技术，撤热段内的撤热管组一般按照图2所示的排布方式，即各个撤热管以直线的方式排布。另一方面，如图1所示，流化床反应器的撤热段内还包括旋风分离器的9的料腿等其他内构件。一般地，所述撤热管包括冷却水入口、直管和冷却水出口、以及使这些管线流体连通的连接管。具体如图1或图4所示，每个撤热管包括冷却水入口3、冷却水出口4、多个直管和用于使任意两个相邻的直管串联并流体连通的连接管件。
根据本发明的一个实施方式，所述撤热管组包括至少1个第一撤热管。在此，所述第一撤热管包括n1(2<n1<30，优选为2<n1<20，更优选为2<n1<10)个平行于所述流化床反应器的中心轴线方向延伸的直管a和n1-1个用于使相邻两个直管a串联并流体连通的连接管件。
根据本发明的一个实施方式，所述第一撤热管的数量为1-4个或1个。
根据本发明的一个实施方式，所述撤热管组包括至少1个第二撤热管。在此，所述第二撤热管包括n2(2<n2<30，优选为2<n2<20，更优选为2<n2<10)个平行于所述流化床反应器的中心轴线方向延伸的直管b和n2-1个用于使相邻两个直管b串联并流体连通的连接管件。
根据本发明的一个实施方式，所述第二撤热管的数量为1-4个或1个。
根据本发明的一个实施方式，设所述撤热段沿着所述流化床反应器中心轴线方向的长度为L(单位是m)，则在所述撤热段的所述长度L的整个区域内沿着垂直于所述流化床反应器中心轴线的方向横切时，获得所述撤热段的横切面。在此，所谓撤热段的横切面，指的是流化床反应器在撤热段处的内轮廓的横切面。作为所述区域，优选在所述反应撤热段中心点上下49％L的区域内，更优选在所述反应撤热段中心点以上45％L以下38％L的区域内，更优选在所述反应撤热段中心点以上40％L以下8％L的区域内。举例而言，所述撤热段的长度L为4-12.5m，优选5.5-11.5m。
根据本发明的一个实施方式，所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)的全部直管a的数量与所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)的全部直管b的数量相同。
根据本发明的一个实施方式，所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)的全部直管b在所述横切面上的外轮廓总周长Lb与所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)的全部直管a在所述横切面上的外轮廓总周长La之间的比值为1.25-2(优选为1.3-2或1.5-2)。在第一撤热管与第二撤热管切换过程中，虽然Lb比La的撤热面积大些，但撤热管a所处的中心区域，其其热传导能力要高于的撤热管b所处的 外周区域,因此，在Lb/La小于1.25时，切换操作时，其撤热能力幅度相当，撤热管组无法满足精细化调节温度的作用。在Lb/La大于2时，撤热面积增加导致撤热能力提高的幅度高于不同撤热管热量传导能力差异导致撤热能力幅度，同样也是无法满足要求的。
根据本发明的一个实施方式，满足|n1-n2|<5(优选|n1-n2|<3)。一个撤热管外轮廓周长为其n个撤热直管外轮廓周长之和或者外轮廓周长直接用n*3.14*D表示(D为撤热直管的平均外径)，通常情况直管数越多，外轮廓周长也越长，在装置运行过程中，其撤热能力也越强。因此，对于撤热管组，|n1-n2|过大，也就意味着第一撤热管与第二撤热管外轮廓周长相差的越大，容易导致撤热管对切换时反应温度的偏移，也或者可以通过设置不同的管外径，|n1-n2|过大，第一撤热管与第二撤热管管外径相差也会大，显然这是不合理的，也是不经济。
根据本发明的一个实施方式，所述直管a的外径(单位是mm)与所述直管b的外径(单位是mm)之比为1-1.8，优选为1-1.5。
根据本发明的一个实施方式，所述直管b的外径(单位是mm)与所述直管a的外径(单位是mm)之比为1-1.8，优选为1-1.5。
根据本发明的一个实施方式，所述直管a的外径各自独立地为80-180mm，优选90-170mm，所述直管a的长度各自独立地为4-13m，优选5-12.0m，并且相邻两个直管a之间的间距为100-700mm，优选150-500mm。
根据本发明的一个实施方式，所述直管b的外径各自独立地为80-180mm，优选90-170mm，所述直管b的长度各自独立地为4-13m，优选5-12.0m，并且相邻两个直管b之间的间距为100-700mm，优选150-500mm。
根据本发明的一个实施方式，1个所述第一撤热管的外轮廓总周长为0.5-17m，优选2.5-11.3m。
根据本发明的一个实施方式，1个所述第二撤热管的外轮廓总周长为0.5-17m，优选2.5-11.3m。
根据本发明的一个实施方式，所述撤热管组包括至少一对(优选1-20对，更优选2-10对或2-5对)撤热管，并且每对所述撤热管由所述至少1个第一撤热管和所述至少1个第二撤热管构成。换句话说，根据本发明的该实施方式，所述撤热管组包括至少一个(优选1-20个，更优选2-10个或2-5个)撤热管对，每个所述撤热管对由所述至少1个第一撤热管和所述至少1个第二撤热管构成。在本说明书下文的描述中，在没有特别明确的情况下，第一撤热管和第二撤热管均指的是同一个撤热管对中的第一撤热管和第二撤热管。本发明不旨在限定在不同的撤热管对中，一个撤热管对中的第一撤热管与另一个撤热管对中的第二撤热管之间的关系，或者一个撤热管对中的第一撤热管与另一个撤热管对中的第一撤热管之间的关系，或者一个撤热管对中的第二撤热管与另一个撤热管对中的第一撤热管之间的关系，或者一个撤热管对中的第二撤热管与另一个撤热管对中的第二撤热管之间的关系。
根据本发明，所述至少1个第一撤热管和所述至少1个第二撤热管不同时工作，而是根据生产操作需要切换工作，也即所述至少1个第一撤热管在进行撤热操作时，所述至少1个第二撤热管处于空闲状态，而所述第一撤热管与第二撤热管，当通过关闭反应器外部冷却盘管与第一撤热管之间的阀门，切断第一撤热管内冷却剂的流通，使撤热操作的第一撤热管处于空闲状态，同时打开反应器外部冷却盘管与第二撤热管之间的阀门，使冷却剂在第二撤热管流体流通，使空闲状态的第二撤热管处于撤热操作状态；与之相反，第一撤热管与第二撤热管同样可以反向切换操作，当通过打开反应器外部冷却盘管与第一撤热管之间的阀门，使第一撤热管内冷却剂的流体流通，使空闲状态的第一撤热管处于撤热操作，同时关闭反应器外部冷却盘管与第二撤热管之间的阀门，切断冷却剂在第二撤热管的流体流通，使撤热操作的第二撤热管处于空闲状态。显然，如前所述，所述至少1个第一撤热管和所述至少1个第二撤热管是同一个撤热管对中的撤热管。
根据本发明，在相同的流化床反应器操作条件下，所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)对所述流化床反应器的反应温度的调节幅度与所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)对所述流化床反应器的反应温度的调节幅度的差异(绝对值)为0.5-3℃(优选1-2℃)。通过如此配制，本发明可以实现在同一个撤热管对内切换撤热管时反应温度的精确控制。
根据本发明的一个优选实施方式，在所述撤热段的横切面内，所述第一撤热管的全部直管a中的大于50％(优选60％以上、更优选为70％以上)的直管a在所述流化床反应器的所述撤热段的横切面的中心部分范围内，且所述第二撤热管的全部直管b中的小于50％(优选40％以下、更优选为30％以下)的直管b在所述横切面的中心部分范围内。例如，当第一撤热管10具有8个直管时，5个以上的直管在所述横切面的中心部分范围，或者当第一撤热管10具有7个直管时，4个以上的直管在所述横切面的中心部分范围。另一方面，例如，当第二撤热管20具有6个直管时，2个以下的直管在所述横切面的中心部分范围，或者当第二撤热管20具有5个直管时，2个以下的直管在所述横切面的中心部分范围。
根据本发明的该优选实施方式，设如图3所示的流化床反应器的撤热段的圆形横切面的半径为R(单位是m)，则所述横切面的中心部分是指距离该圆形横切面的圆心一定距离以内的范围(即图3中的虚线以内的范围)，而所述横切面的外围区域是指中心部分以外的区域(即图3中的虚线至反应器壁1的范围)。根据本发明的一个实施方式，所述横切面的中心部分是指距离横切面的圆心3/4R以内的圆形区域，优选为距离横切面的圆心2/3R以内的圆形区域，更优选为距离横切面的圆心1/2R以内的圆形区域，还更优选为距离横切面的圆心1/3R以内的圆形区域。举例而言，所述半径R为5-29m，优选7-20m。
根据本发明的一个实施方式，在存在多个时，至少2个(优选 全部)所述第一撤热管的冷却水入口在所述撤热段内合并成一个冷却水入口集管。换句话说，多个所述撤热管(称为支管)共用一个冷却水入口。根据本发明，所述冷却水入口集管穿过所述流化床反应器的器壁与外界的冷却水提供源流体连通，由此通过该冷却水入口集管向各个支管供应冷却水。
根据本发明的一个实施方式，在存在多个时，至少2个(优选全部)所述第二撤热管的冷却水出口在所述撤热段内合并成一个冷却水出口集管。换句话说，多个所述撤热管(称为支管)共用一个冷却水出口。根据本发明，所述冷却水出口集管穿过所述流化床反应器的器壁与外界的冷却水接受装置流体连通，由此通过该冷却水出口集管从各个支管向外界输送撤热之后的冷却水(一般还包含蒸汽)。
根据本发明的一个实施方式，在存在多个时，至少2个(优选全部)所述第二撤热管的冷却水入口在所述撤热段内合并成一个冷却水入口集管。换句话说，多个所述撤热管(称为支管)共用一个冷却水入口。根据本发明，所述冷却水入口集管穿过所述流化床反应器的器壁与外界的冷却水提供源流体连通，由此通过该冷却水入口集管向各个支管供应冷却水。
根据本发明的一个实施方式，在存在多个时，至少2个(优选全部)所述第二撤热管的冷却水出口在所述撤热段内合并成一个冷却水出口集管。换句话说，多个所述撤热管(称为支管)共用一个冷却水出口。根据本发明，所述冷却水出口集管穿过所述流化床反应器的器壁与外界的冷却水接受装置流体连通，由此通过该冷却水出口集管从各个支管向外界输送撤热之后的冷却水(一般还包含蒸汽)。
图4和图5是本发明的撤热管集管的布置示意图。从图中可以看到，多个撤热管的冷却水出/入口汇总为一个集管。
根据本发明的一个实施方式，所述集管(比如所述冷却水入口集管或所述冷却水出口集管)的横截面积与其所对应的所述多个支 管(一般以所述多个支管的冷却水入口或冷却水出口为计)的横截面积之和的比值是0.5-1，优选为0.55-0.95，更优选为0.6-0.9。
根据本发明的一个实施方式，还涉及一种撤热管组，其特征在于，所述撤热管组设置在流化床反应器的撤热段内，所述撤热段设置于所述流化床反应器的流化床层内，所述撤热管组包括：至少1个第一撤热管，该第一撤热管包括n1(2<n1<30,优选为2<n1<20，更优选为2<n1<10)个平行于所述流化床反应器的中心轴线方向延伸的直管a和n1-1个用于使所述n1个直管串联并流体连通的连接管件；和至少1个第二撤热管，该第二撤热管包括n2(2<n1<30,优选为2<n1<20，更优选为2<n1<10)个平行于所述流化床反应器的中心轴线方向延伸的直管b和n2-1个用于使所述n2个直管串联并流体连通的连接管件，其中，在所述撤热段的任意位置处沿着垂直于所述流化床反应器中心轴线的方向横切所获得的横切面内，所述第一撤热管的全部直管a中的大于50％(优选60％以上、更优选为70％以上)的直管a在所述流化床反应器的所述撤热段的横切面的中心部分范围内，且所述第二撤热管的全部直管b中的小于50％(优选40％以下、更优选为30％以下)的直管b在所述横切面的中心部分范围内，并且其中，所述第二撤热管的全部直管b的外轮廓总周长Lb与所述第一撤热管的全部直管a的外轮廓总周长La之间的比值为1.5-2。
根据本发明的一个实施方式，还涉及一种流化床反应器，其从顶到底顺次包括封头、稀相区、撤热段、预反应段和锥体。在此，在所述撤热段中设置本说明书前文所述的撤热管组。
根据本发明的一个实施方式，还涉及一种流化床反应器的温度控制方法。在此，所述流化床反应器优选是本说明书前文所述的流化床反应器。
根据本发明的一个实施方式，所述温度控制方法包括在反应过程中，将所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)切换至所述第二撤热管(在存在多个时，为多个所述第 二撤热管合在一起)，以将所述流化床反应器的反应温度升高或降低0.5-3℃(优选1-2℃)。
根据本发明的一个实施方式，还涉及一种不饱和腈的制造方法，包括在流化床反应器中使烯烃(比如丙烯)发生氨氧化反应而生成不饱和腈(比如丙烯腈)的步骤。在此，可以按照本说明书前文所述的温度控制方法对所述流化床反应器进行温度控制，以维持所述流化床反应器的反应温度基本上恒定，以实现反应温度的精细调节。
根据本发明的一个实施方式，还涉及一种不饱和腈的制造方法，包括在流化床反应器中使烯烃(比如丙烯)发生氨氧化反应而生成不饱和腈(比如丙烯腈)的步骤。在此，所述流化床反应器优选是本说明书前文所述的流化床反应器。
根据本发明的一个实施方式，所述氨氧化反应可以按照本领域常规已知的任何方式和任何方法进行，这些信息对于本领域技术人员而言是已知的，本文在此不再赘述。虽然如此，作为所述氨氧化反应的操作条件，具体比如可以举出丙烯/氨气/空气(以分子氧计)的摩尔比一般为1：1.1-1.3：1.8-2.0，反应温度一般为420-440℃，反应压力(表压)一般为0.03-0.14MPa，催化剂重时空速一般为0.04-0.15h -1。
实施例
以下将通过实施例和比较例对本发明进行进一步的详细描述，但本发明不限于以下实施例。
在以下的实施例和比较例中，丙烯腈收率及丙烯转化率可按以下公式计算：
丙烯腈收率：AN％＝C AN/ΣC*100
丙烯转化率：Cc 3％＝(1-Cc 3出/Cc 3进)*100
其中：
C AN:反应器出口气体中AN含的碳摩尔数(mol)
ΣC:反应器出口气体碳摩尔总数(mol)
Cc 3出:反应器出口气体中C 3含的碳摩尔数(mol)
Cc 3出:反应器进口气体中C 3含的碳摩尔数(mol)。
实施例1
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共584个，共分为62个撤热管。共有4组撤热管对，每组撤热管对中1个撤热管为由4个直管a串联组成的第一撤热管，另一个撤热管为由4个直管b串联组成的第二撤热管。支管a的外径与支管b的外径之比为0.53，并且构成第二撤热管的全部直管的外轮廓总周长与构成第一撤热管的直管的外轮廓总周长之比为1.89。
在丙烯进料量为11800NM 3/h，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过第一撤热管与第二撤热管之间的切换，能够以2.0℃的升温或降温幅度精细调节反应器温度。
实施例2
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共584个，共分为62个撤热管。共有4组撤热管对，每组撤热管对中1个撤热管为由6个直管a串联组成的第一撤热管，另一个撤热管为由6个直管b串联组成的第二撤热管。支管a的外径与支管b的外径之比为0.66，并且构成第二撤热管的全部直管的外轮廓总周长与构成第一撤热管的直管的外轮廓总周长之比为1.52。
在丙烯进料量为11800NM 3/h，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过第一撤热管与第二撤热管之间的切换，能够以1.3℃的升温或降温幅度精细调节反应器温度。
实施例3
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共584个，共分为62个撤热管。共有2组撤热管对，其中撤热管对是由一个撤热管由8个直管a串联组成的第一撤热管，该第一撤热管共5个直管a位于反应器撤热段横截面中距离圆心的2/3R的范围内；另一个撤热管是由8个直管b串联组成的第二撤热管，该第二撤热管的6个直管b位于反应器撤热段横截面中距离圆心的2/3R的范围之外。支管b的外径与支管a的外径之比为1.54，并且构成第二撤热管的全部直管的外轮廓总周长与构成第一撤热管的直管的外轮廓总周长之比为1.54。
在丙烯进料量为11800NM 3/h，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过撤热管组的第一撤热管与第二撤热管之间的切换，能够以1.4℃的升温或降温幅度精细调节反应器温度。
实施例4
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共732个，共分为70个撤热管。有4组撤热管对，其中一个撤热管由12个直管a串联和10个直管a串联组成的第一撤热管，另一个撤热管由12个直管b串联和10个直管b串联组成的第二撤热管；支管b与支管a的外径之比为1.35，并且构成第二撤热管的全部直管的外轮廓总周长与构成第一撤热管的直管的外轮廓总周长之比为1.35。
在丙烯进料量为11800NM 3/h，此时的满负荷丙烯处理量为349kg丙烯/m 2/小时，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过撤热管组的第一撤热管 与第二撤热管之间的切换，能够以1.6℃的升温或降温幅度精细调节反应器温度。
实施例5
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共732个，共分为70个撤热管。共有5组撤热管对，其中撤热管对是由一个撤热管由12个直管a串联和由8个直管a串联组成的第一撤热管，该第一撤热管共14个直管a位于反应器撤热段横截面中距离圆心的2/3R的范围内；另一个撤热管是由10个直管b串联和由10个直管b串联组成的第二撤热管，该第二撤热管的15个直管b位于反应器撤热段横截面中距离圆心的2/3R的范围之外。支管b的外径与支管a的外径之比为1.69，并且构成第二撤热管的全部直管的外轮廓总周长与构成第一撤热管的直管的外轮廓总周长之比为1.69。
在丙烯进料量为11800NM 3/h，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过撤热管组的第一撤热管与第二撤热管之间的切换，能够以1.8℃的升温或降温幅度精细调节反应器温度。
实施例6
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共732个，共分为70个撤热管。有4组是由2个撤热管组并联连接，为2组撤热管对，其中一个撤热管由8个直管a串联和8个直管a串联组成的第一撤热管，撤热管a外径为89mm，另一个撤热管由由8个直管b串联和8个直管b串联组成的第二撤热管；撤热管外径b为120mm，支管a与支管b的外径之比为0.74，并且构成第二撤热管的全部直管的外轮廓总周长与构成第一撤热管的直管的外轮廓 总周长之比为1.35。撤热管b入口集管外径为140mm,撤热管b出口集管外径为150mm,入口集管截面积与撤热支管横截面积之和比值为0.68，出口集管截面积与撤热支管横截面积之和比值为0.78；撤热管a入口集管外径为120mm,撤热管a出口集管外径为120mm,入口集管截面积与撤热支管横截面积之和比值为0.90，出口集管截面积与撤热支管横截面积之和比值为0.90。
在丙烯进料量为11800NM 3/h，此时的满负荷丙烯处理量为349kg丙烯/m 2/小时，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过撤热管组的第一撤热管与第二撤热管之间的切换，能够以1.3℃的升温或降温幅度精细调节反应器温度。
比较例1
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共584个，共分为60个撤热管。共有4组撤热管对，每组撤热管对中1个撤热管为由8个直管a串联组成的第一撤热管，另一个撤热管为由8个直管b串联组成的第二撤热管，支管b的外径与支管a的外径之比为1.2，并且构成第二撤热管的全部直管b的外轮廓总周长与构成第一撤热管的直管a的外轮廓总周长之比为1.20。
在丙烯进料量为11800NM 3/h，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过撤热管组的第一撤热管与第二撤热管之间的切换，反应器温度的变化幅度为0.7℃，没有出现明显的升温或降温过程。
比较例2
流化床反应器直径为9米，装填180吨牌号为中国石化上海石油化工研究院SANC系列丙烯腈催化剂，内设高度相同的直管共584个，共分为60个撤热管。共有2组撤热管对，每组撤热管对中1 个撤热管为由11个直管a串联组成的第一撤热管，另一个撤热管为由11个直管b串联组成的第二撤热管，支管b的外径与支管a的外径之比为2.2，并且构成第二撤热管的全部直管b的外轮廓总周长与构成第一撤热管的直管a的外轮廓总周长之比为2.20。
在丙烯进料量为11800NM 3/h，反应温度为430℃，反应压力为0.04Mpa，丙烯：氨：空气为1：1.2：9.6条件下，通过撤热管组的第一撤热管与第二撤热管之间的切换，只能够以3.3℃的升温或降温幅度粗略调节反应器温度。

Claims (12)

  1. 一种撤热管组(特别是撤热水管组)，其特征在于，所述撤热管组被构造为设置在流化床反应器的撤热段内，所述撤热段设置于所述流化床反应器的流化床层内，所述撤热管组包括：
    至少1个第一撤热管，所述第一撤热管包括n1(2<n1<30，优选为2<n1<20，更优选为2<n1<10)个平行于所述流化床反应器的中心轴线方向延伸的直管a和n1-1个用于使相邻两个直管a串联并流体连通的连接管件；和
    至少1个第二撤热管，所述第二撤热管包括n2(2<n2<30，优选为2<n2<20，更优选为2<n2<10)个平行于所述流化床反应器的中心轴线方向延伸的直管b和n2-1个用于使相邻两个直管b串联并流体连通的连接管件，
    在所述撤热段的任意位置处(设所述撤热段沿着所述流化床反应器中心轴线方向的长度为L(单位是m)，优选在所述撤热段的所述长度L的整个区域内，更优选在所述反应撤热段中心点上下49％L的区域内，更优选在所述反应撤热段中心点以上45％L以下38％L的区域内，更优选在所述反应撤热段中心点以上40％L以下8％L的区域内)沿着垂直于所述流化床反应器中心轴线的方向横切而获得横切面，
    其中，所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)的全部直管a的数量与所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)的全部直管b的数量相同，并且所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)的全部直管b在所述横切面上的外轮廓总周长Lb与所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)的全部直管a在所述横切面上的外轮廓总周长La之间的比值为1.25-2(优选为1.3-2或1.5-2)。
  2. 权利要求1所述的撤热管组，其特征在于，满足|n1-n2|<5 (优选|n1-n2|<3)。
  3. 权利要求1所述的撤热管组，其特征在于，所述第一撤热管的全部直管a中的大于50％(优选60％以上、更优选为70％以上)的直管a在所述流化床反应器的所述撤热段的横切面的中心部分范围内，且所述第二撤热管的全部直管b中的小于50％(优选40％以下、更优选为30％以下)的直管b在所述横切面的中心部分范围内，和/或，设所述横切面的半径为R(单位是m)，则所述中心部分范围为距所述横切面的圆心3/4R范围内(优选为2/3R范围内，更优选为1/2R范围内，还更优选为1/3R范围内)。
  4. 权利要求1所述的撤热管组，其特征在于，所述直管a的外径(单位是mm)与所述直管b的外径(单位是mm)之比为1-1.8，优选为1-1.5；或者，所述直管b的外径(单位是mm)与所述直管a的外径(单位是mm)之比为1-1.8，优选为1-1.5。
  5. 权利要求1所述的撤热管组，其特征在于，所述直管a的外径各自独立地为80-180mm，优选90-170mm，所述直管a的长度各自独立地为4-13m，优选5-12.0m，并且相邻两个直管a之间的间距为100-700mm，优选150-500mm，和/或，所述直管b的外径各自独立地为80-180mm，优选90-170mm，所述直管b的长度各自独立地为4-13m，优选5-12.0m，并且相邻两个直管b之间的间距为100-700mm，优选150-500mm，和/或，1个所述第一撤热管的外轮廓总周长为0.5-17m，优选2.5-11.3m，和/或，1个所述第二撤热管的外轮廓总周长为0.5-17m，优选2.5-11.3m。
  6. 权利要求1所述的撤热管组，其特征在于，所述撤热段的长度L为4-12.5m，优选5.5-11.5m，和/或，所述半径R为5-29m，优选7-20m，和/或，所述第一撤热管的数量为1-4个或1个，和/或，所述第二撤热管的数量为1-4个或1个，和/或，所述撤热管组包括至少一对(优选1-20对，更优选2-10对或2-5对)撤热管，并且每对所述撤热管由所述至少1个第一撤热管和所述至少1个第二撤热管构成。
  7. 权利要求1所述的撤热管组，其特征在于，在相同的流化床反应器操作条件下，所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)对所述流化床反应器的反应温度的调节幅度与所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)对所述流化床反应器的反应温度的调节幅度的差异(绝对值)为0.5-3℃(优选1-2℃)，和/或，在存在多个时，至少2个(优选全部)所述第一撤热管的冷却水入口在所述撤热段内合并成一个冷却水入口集管，和/或，在存在多个时，至少2个(优选全部)所述第一撤热管的冷却水出口在所述撤热段内合并成一个冷却水出口集管，和/或，在存在多个时，至少2个(优选全部)所述第二撤热管的冷却水入口在所述撤热段内合并成一个冷却水入口集管，和/或，在存在多个时，至少2个(优选全部)所述第二撤热管的冷却水出口在所述撤热段内合并成一个冷却水出口集管。
  8. 一种流化床反应器，其特征在于，从顶到底顺次包括封头、稀相区、撤热段、预反应段和锥体，其中在所述撤热段中设置权利要求1所述的撤热管组。
  9. 权利要求8所述的流化床反应器的温度控制方法，其特征在于，包括在反应过程中，将所述第一撤热管(在存在多个时，为多个所述第一撤热管合在一起)切换至所述第二撤热管(在存在多个时，为多个所述第二撤热管合在一起)，以将所述流化床反应器的反应温度升高或降低0.5-3℃(优选1-2℃)。
  10. 一种不饱和腈的制造方法，包括在权利要求8所述的流化床反应器中使烯烃(比如丙烯)发生氨氧化反应而生成不饱和腈(比如丙烯腈)的步骤。
  11. 一种不饱和腈的制造方法，包括在流化床反应器中使烯烃(比如丙烯)发生氨氧化反应而生成不饱和腈(比如丙烯腈)的步骤，其中按照权利要求9所述的温度控制方法对所述流化床反应器进行温度控制。
  12. 权利要求10或11所述的制造方法，其特征在于，丙烯/ 氨气/空气(以分子氧计)的摩尔比为1：1.1-1.3：1.8-2.0，反应温度为420-440℃，反应压力(表压)为0.03-0.14MPa，催化剂重时空速为0.04-0.15h -1。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3983927A (en) * 1975-06-25 1976-10-05 Dorr-Oliver Incorporated Heat exchanger for fluidized bed reactor
CN101773808A (zh) * 2007-10-19 2010-07-14 杭州林达化工技术工程有限公司 一种组合反应设备
CN102531958A (zh) * 2011-11-18 2012-07-04 中国石油化工股份有限公司 流化床反应器生产芳腈的方法
CN104941529A (zh) * 2014-03-31 2015-09-30 英尼奥斯欧洲股份公司 用于氧化反应器或氨氧化反应器的冷却盘管设计
CN106492711A (zh) * 2015-09-06 2017-03-15 中国石油化工股份有限公司 反应器温度的调节装置和调节方法
CN107413285A (zh) * 2016-05-24 2017-12-01 英尼奥斯欧洲股份公司 氨氧化反应器控制
CN108940137A (zh) * 2017-05-19 2018-12-07 旭化成株式会社 流化床反应装置及α,β-不饱和腈的制造方法
CN110787737A (zh) * 2019-10-24 2020-02-14 中石化宁波工程有限公司 一种等温变换反应器

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6143915A (en) * 1998-11-23 2000-11-07 Uop Llc Reaction process in hybrid reactor for propylene ammoxidation
CN101507907B (zh) * 2008-02-15 2012-01-25 旭化成化学株式会社 流化床反应器的温度控制方法
CN102010350B (zh) * 2009-09-07 2013-12-18 中国石油化工集团公司 增加丙烯腈或甲基丙烯腈生产能力的方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3983927A (en) * 1975-06-25 1976-10-05 Dorr-Oliver Incorporated Heat exchanger for fluidized bed reactor
CN101773808A (zh) * 2007-10-19 2010-07-14 杭州林达化工技术工程有限公司 一种组合反应设备
CN102531958A (zh) * 2011-11-18 2012-07-04 中国石油化工股份有限公司 流化床反应器生产芳腈的方法
CN104941529A (zh) * 2014-03-31 2015-09-30 英尼奥斯欧洲股份公司 用于氧化反应器或氨氧化反应器的冷却盘管设计
CN106492711A (zh) * 2015-09-06 2017-03-15 中国石油化工股份有限公司 反应器温度的调节装置和调节方法
CN107413285A (zh) * 2016-05-24 2017-12-01 英尼奥斯欧洲股份公司 氨氧化反应器控制
CN108940137A (zh) * 2017-05-19 2018-12-07 旭化成株式会社 流化床反应装置及α,β-不饱和腈的制造方法
CN110787737A (zh) * 2019-10-24 2020-02-14 中石化宁波工程有限公司 一种等温变换反应器

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