WO2022214067A1 - 一种撤热管组、反应负荷提高方法以及不饱和腈的制造方法 - Google Patents

一种撤热管组、反应负荷提高方法以及不饱和腈的制造方法 Download PDF

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Publication number
WO2022214067A1
WO2022214067A1 PCT/CN2022/085766 CN2022085766W WO2022214067A1 WO 2022214067 A1 WO2022214067 A1 WO 2022214067A1 CN 2022085766 W CN2022085766 W CN 2022085766W WO 2022214067 A1 WO2022214067 A1 WO 2022214067A1
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Prior art keywords
heat removal
section
heat
pipes
pipe
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PCT/CN2022/085766
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English (en)
French (fr)
Inventor
赵乐
吴粮华
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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 CN202110382764.1A external-priority patent/CN115337871A/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 KR1020237037349A priority Critical patent/KR20230169185A/ko
Priority to EP22784133.5A priority patent/EP4321243A1/en
Priority to JP2023561321A priority patent/JP2024513886A/ja
Publication of WO2022214067A1 publication Critical patent/WO2022214067A1/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
    • 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
    • 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
    • F28D21/00—Heat-exchange apparatus not covered by any of the groups F28D1/00 - F28D20/00
    • F28D2021/0019—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for
    • F28D2021/0022—Other heat exchangers for particular applications; Heat exchange systems not otherwise provided for for chemical reactors

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 method for increasing the reaction load by utilizing the heat removal tube group and its application in the production of unsaturated nitrile.
  • 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 oxygen-containing gas distribution plate
  • acryl ammonia distributor heat extraction pipe
  • cyclone separator cyclone separator
  • the improved performance of the ammoxidation catalyst allows the fluidized bed reactor (even with the same size) to operate at a larger (eg 50% higher) reaction load, i.e. the feedstock propylene, ammonia, oxygen-containing gas feeds are increased by 50%, resulting in The heat release of the reaction is increased by 50%.
  • the heat extraction pipes are arranged parallel or perpendicular to each other, and the intervals are the same when they are parallel to each other.
  • the conventional heat removal pipe is that the upper connector and the lower connector and the straight pipe of the heat removal pipe are projected on the same line on the cross section of the reactor, and the upper connector and the lower connector form 180°; at least one upper connector and lower connector of the special-shaped heat removal tube At a certain angle, along the running direction of the fluid main body, the projection of the fluid-connected straight pipes on the cross-section of the reactor is two closely adjacent straight lines; since the special-shaped heat extraction pipe has a tighter connection than the conventional heat extraction pipe, the With the increase in the number of special-shaped heat removal pipes replacing conventional heat removal pipes, the continuous improvement of heat removal capacity is also more conducive to breaking large air bubbles.
  • the present invention is completed based on this finding, by changing the structural type and number of heat removal pipes in the fluidized bed reactor to enhance the heat removal capability and fluidization efficiency of the fluidized bed reactor.
  • the conventional heat removal pipe and the special-shaped heat removal pipe are configured according to a predetermined ratio, so as to realize the high efficiency and long-term stable operation of the device.
  • 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 a heat-extraction section of a fluidized bed reactor, and the heat-extraction pipe group comprises at least 10 (preferably 10 to 100, more preferably 20-80) heat evacuation pipes, the heat evacuation pipes include N (N is greater than or equal to 3, preferably, N is 3 to 30, more preferably N is 3 to 20) Straight pipes and N-1 connecting pipe fittings for connecting any two adjacent straight pipes in series and in fluid communication,
  • transverse section A when transversely intersecting the direction perpendicular to the central axis of the fluidized bed reactor, the transverse section of the heat removal section (called transverse section A) is obtained,
  • the number is at least 1 (preferably 1, 2 or 3, or at least 20%, at least 50% or at least 65% of the total number of heat withdrawal pipes in the heat withdrawal pipe group) and at most in the heat withdrawal pipe group Among 88% (preferably 75% or 70%) of the total number of heat removal pipes (referred to as special-shaped heat removal pipes), at least 1 (preferably, at least 2, 3 or 4, and at most the special-shaped heat removal pipes) 80%, 90% or 100% of the total number of connecting pipe fittings in the heat pipe) connecting pipe fittings (preferably excluding the first connecting pipe fitting of the special-shaped heat extraction pipe) projected on the transverse plane A
  • the extension line of the central axis is at least 1
  • the included angle of the extension line of the projected central axis of each of the other connecting pipe pieces (preferably the other connecting pipe pieces on the special-shaped heat extraction pipe that is directly upstream of the fluid communication of the connecting pipe piece) on the transverse plane A is greater than 0° and less than 180° ° (preferably 30°-150°, more preferably 60°-120
  • the heat removal pipe group according to any one of the foregoing or the following aspects is characterized in that, if the number of all the straight pipes in the heat removal pipe group is set in the cross section A, the number of all the straight pipes in the heat removal pipe group is Nt, then the transverse The number of straight pipes Nt/S1 per unit area of the cutting plane A is 4-16 pieces/m 2 (preferably 5-14 pieces/m 2 , more preferably 7-13 pieces/m 2 ), and/or, the The profile of the cross section A is circular, oval or oval, preferably circular or substantially circular, and/or, the inner and outer profiles of the cross section of the straight tube are circular, oval or oval shape, preferably circular or substantially circular.
  • saturated steam of 1-10MPa preferably saturated steam of 2-8MPa, more preferably saturated steam of 3-5MPa
  • the heat withdrawal capacity of the heat withdrawal pipe group is 0.5-3.0t saturated steam/unit cross-sectional area (m 2 )/hour, preferably 1.0-2.8t saturated Steam
  • any one of the connecting pipe fittings is on the cross section A
  • the included angle between the extension line of the projected central axis on the heat extraction pipe and the extension line of the projected central axis of the other connecting pipe fittings directly upstream or directly downstream of the fluid communication of the connecting pipe fitting on the transverse plane A is: 180°
  • the heat evacuation pipe includes cooling water inlets, and a plurality of (preferably 2-8, 2-6 or 2-4) cooling water inlets of the heat evacuation pipe are located in the heat evacuation pipe.
  • the section is merged into a cooling water inlet header, and/or, the heat withdrawal pipe includes a cooling water outlet, and a plurality (preferably 2-8, 2-6 or 2-4) of the heat withdrawal pipe
  • the cooling water outlets are combined into a cooling water outlet header within the heat withdrawal section.
  • the distance between the two straight pipes is 100-700mm, preferably 150-300mm, and/or the length H of the heat removal section is 4-13m (preferably 5-12m).
  • L1/S1 is 1.0-2.5 m ⁇ 1 (excluding the numerical endpoint 2.5), preferably 1.4-2.2m -1 , or
  • L1/S1 is 1.8-4.6 m -1 , preferably 2.0-4.1 m - 1 , or
  • L1/S1 is 2.5-6.0 m -1 , preferably 2.9-5.3 m -1 .
  • 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.
  • 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 described in any one of the foregoing or the following aspects step.
  • olefin such as propylene
  • unsaturated nitrile such as acrylonitrile
  • a method for increasing the load of a fluidized-bed reactor wherein the full-load hourly propylene processing capacity of the fluidized-bed reactor is 140-290 kg propylene/m 2 of the cross section A (excluding the numerical endpoint 290) , and L1/S1 is 1.0-2.5m -1 (excluding numerical endpoint 2.5), the load increasing method includes increasing the full-load hourly propylene throughput of the fluidized bed reactor to 290-445 kg propylene/m 2 Simultaneously with the cross section A, increase the L1/S1 to 2.5-6.0 m -1 , preferably to 2.9-5.3 m -1 .
  • 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
  • ammoxidizing olefin such as propylene
  • unsaturated nitrile such as acrylonitrile
  • 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.
  • Figure 3 is a schematic top view of the fluidized bed reaction heat removal tube group of the present invention.
  • 4A-4D are schematic diagrams of the arrangement of the heat removal pipes of the heat removal pipe group of the present invention.
  • FIG. 5 is a graph of pressure pulsation intensity.
  • FIG 6 and 7 are schematic diagrams of the arrangement of the heat extraction pipe headers of the present invention.
  • the production capacity of the target product of the device can be improved, the demand for increasing the reaction load can be fully met, and the operation cost of the device can be reduced.
  • the heat removal pipe group of the present invention a tighter arrangement is realized, that is, more straight pipes are arranged in the cross-sectional area of the reactor, thereby enhancing the heat removal capability.
  • the change of the flow pattern in the fluidized bed can be accelerated, and the mass transfer efficiency can be improved.
  • the growth of bubbles can be effectively suppressed, so as to achieve the purpose of improving the conversion rate of the raw material gas and increasing the yield of the target reaction product.
  • the degree of back-mixing of the gas-solid phase can be reduced, and the generation of deep oxidation products can be reduced.
  • the heat transfer efficiency can be improved and the operation period of the device can be prolonged.
  • 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 some exothermic stage of the 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 extraction pipe group includes at least 10 (preferably 10 to 100, more preferably 20-80) heat extraction pipes.
  • 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.
  • the heat evacuation pipe includes N (N is greater than or equal to 3, preferably, N is 3 to 30, more preferably N is 3 to 20) straight pipes and the straight pipes used to make any two adjacent ones N-1 connecting pipe fittings where the pipes are connected in series and in fluid communication.
  • each heat removal pipe 2 includes: a cooling water inlet 3, a cooling water outlet 4, at least three adjacent straight pipes, and a Connect the fittings.
  • lower connecting pipe 5" when the connecting pipe connecting any two straight pipes is located below the straight pipes (hereinafter, sometimes referred to as "lower connecting pipe 5"), the other adjacent connecting pipe is located at the bottom of the straight pipe. Above the straight pipe (hereinafter, sometimes simply referred to as “lower connecting pipe fitting 6").
  • each straight pipe shows a positional relationship of upstream and downstream.
  • the adjacent and upstream positional relationship is referred to as direct upstream
  • the adjacent and downstream positional relationship is referred to as direct downstream.
  • 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 length of the heat withdrawal section along the central axis direction of the fluidized bed reactor as H (unit is m), then the entire length H of the heat withdrawal section is When the area is crossed along the direction perpendicular to the central axis of the fluidized-bed reactor, the cross-section of the heat withdrawal section (called cross-section A) is obtained.
  • 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 it is preferably within a region of 49% H above and below the center point of the reaction heat removal section, more preferably within a region of 45% H and lower than 38% H above the center point of the reaction heat removal section, and more preferably within In the area of 40% H and below 8% H above the center point of the reaction heat removal section.
  • the heat extraction pipe group includes special-shaped heat extraction pipes.
  • the number of the special-shaped heat removal pipes is at least 1, preferably 1, 2 or 3, or at least 20% of the total number of heat removal pipes in the heat removal pipe group, at least 50% or at least 65%.
  • the number of the special-shaped heat removal pipes is at most 88% of the total number of heat removal pipes in the heat removal pipe group, preferably 75% or 70%.
  • the so-called special-shaped heat extraction pipe refers to the extension of the central axis of the projection of at least one connecting pipe (referred to as a special connecting pipe) included in the cross section A and at least one
  • the included angle (the included angle A) of the extension line of the projected central axis of the other connecting pipe pieces on the transverse plane A is greater than 0° and less than 180°.
  • the included angle A is preferably 30°-150°, more preferably 60°-120°. From the viewpoint of achieving the most excellent technical effect of the present invention, the included angle A is most preferably about 90°, so as to realize the close arrangement of the heat-extracting straight pipes.
  • the number of the special connecting pipes in a special-shaped heat extraction pipe preferably at least 2, 3 or 4, and at most 80%, 90% or 100% of the total number of connection pipes in the special-shaped heat extraction pipe.
  • the number of the special connecting pipes is preferably 100% of the total number of connecting pipes in the special-shaped heat extraction pipe, so that the heat extraction pipes are arranged in parallel with each other and at the same interval, and at the same time, it is ensured that the device has sufficient Repair channel.
  • the connecting pipe described here generally does not include the first connecting pipe of the special-shaped heat extraction pipe.
  • the included angle A1 can be any value, such as 30°-180°, 60°-180°, 90° or 180°.
  • the included angle A1 is also preferably 90°.
  • the straight pipes and the connecting pipes in the same heat extraction pipe 2 can be arranged, for example, according to the arrangement shown in FIGS. 4A-4D .
  • the outer contour of the cross-section of the straight pipe of the heat withdrawal pipe 2 in the heat withdrawal pipe group is substantially circular, and the circumference of the outer contour is 3.14 ⁇ D.
  • D is the diameter of the outer contour of the straight pipe. Therefore, in the cross-section of the heat removal section as shown in FIG. 3, the sum L1 of the outer contour perimeters of the cross-sections of all the straight pipes of the heat-removal pipe group is the total length of all straight pipes in the cross-section of the heat removal section. The sum of the outer contour perimeters of the tubes.
  • the area of the cross section A is set to be S1 (unit is m 2 ), and the outside of the cross section of all the straight pipes of the heat removal pipe group on the cross section A is set
  • the sum of the contour perimeters is L1 (unit is m)
  • L1/S1 is 1.0-6.0 m -1 (preferably 2.4-5.6 m -1 , more preferably 2.9-5.3 m -1 ).
  • L1/S1 represents the arrangement density of all heat-extracting pipes (or straight pipes) on the cross section A, which exists in the optimum range for the realization of the technical effect of the present invention.
  • the L1/S1 layout density is lower than 1.0, the operation reaction load of the device is low.
  • the production cost is high and the economy is poor.
  • the L1/S1 layout density is higher than 6.0, it can operate at a high reaction load to meet more reactions. Due to the requirement of heat removal, the number of special-shaped heat removal pipes in the reactor will increase, which is not conducive to the stability of the reaction temperature during the operation, or the space for maintenance and repair is squeezed.
  • the heat withdrawal pipe group is arranged in the heat withdrawal section of the fluidized bed reactor, and the heat withdrawal pipe group includes at least one (preferably 10 to 100, more preferably 20-80) heat removal pipes
  • the heat removal pipes include N (N greater than or equal to 3, preferably, N is 3 to 30, more preferably N is 3 to 20) straight pipes and used for N-1 connecting pipe fittings for connecting any two adjacent straight pipes in series and in fluid communication, wherein the length of the heat removal section along the central axis direction of the fluidized bed reactor is set as H (unit is m ), then in the entire area of the length H of the heat removal section, (preferably in the area of 49% H above and below the center point of the reaction heat removal section, more preferably 45% above the center point of the reaction heat removal section %H and below 38%H, more preferably above 40%H and below 8%H of the center point of the reaction heat removal section) transversely along the direction perpendicular to
  • the area S1 is 20-700 m 2 (preferably 35-350 m 2 ).
  • the L1 is 20-4200m, preferably 87.5-1225m.
  • the number of all the straight pipes in the heat evacuation pipe group is Nt
  • the number of straight pipes per unit area of the cross section A is Nt/ S1 is 4-16 pieces/m 2 (preferably 5-14 pieces/m 2 , more preferably 7-13 pieces/m 2 ).
  • Nt/S1 also represents the arrangement density of the heat removal pipes (or straight pipes) on the cross section A, which exists in the optimum range for the realization of the technical effect of the present invention.
  • the Nt/S1 arrangement density is lower than 4, it is not conducive to breaking the bubbles for the fluidized bed, so that more raw gas is taken out of the reactor without participating in the reaction, which affects the reaction result.
  • the Nt/S1 arrangement density When it is higher than 16, it can also meet the high-load operation of the reaction, but there is a risk that the increase of the special-shaped heat extraction pipe will lead to the instability of the reaction temperature during the operation, and the risk of squeezing the maintenance space.
  • the profile of the cross section A is circular, elliptical or oval, preferably circular or substantially circular.
  • the inner and outer contours of the cross-section of the straight pipe are circular, elliptical or oval, preferably circular or substantially circular.
  • the heat removal pipe group can recover saturated steam of 1-10 MPa, preferably saturated steam of 2-8 MPa, more preferably saturated steam of 3-5 MPa.
  • the heat withdrawal capacity of the heat withdrawal pipe group is 0.5-3.0t saturated steam/unit cross-sectional area (m 2 )/hour, preferably 1.0-2.8t saturated steam/unit Cross-sectional area (m 2 )/hour, more preferably 1.2-2.4t saturated steam/unit cross-sectional area (m 2 )/hour, wherein the unit cross-sectional area refers to the unit area of the cross section A.
  • the heat removal tube group of the present invention can recover more saturated steam, thereby showing stronger heat removal capacity and meeting the requirements of high reaction load.
  • the heat extraction pipe group further includes a conventional heat extraction pipe, and the conventional heat extraction pipe and the special-shaped heat extraction pipe together constitute the heat extraction pipe group.
  • any extension of the central axis of the projection of any connecting pipe on said transverse plane A is connected to other connections on the heat extraction pipe directly upstream or directly downstream of the fluid communication of the connecting pipe
  • the included angle of the extension line of the central axis of the projection of the pipe fitting on the transverse plane A is 180°.
  • all the straight pipes are in the same plane.
  • heat removal pipes in their meaning cover both special-shaped heat removal pipes and conventional heat removal pipes, unless explicitly stated.
  • the cooling water inlets of a plurality (preferably 2-8, 2-6 or 2-4) of the heat withdrawal pipes are combined into a cooling water inlet set in the heat withdrawal section Tube.
  • the plurality of heat evacuation 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 heat withdrawal pipe through the cooling water inlet header.
  • the heat removal pipe (referred to as the heat removal branch pipe) here can be a conventional heat removal pipe, a special-shaped heat removal pipe or any combination thereof, which is not particularly limited.
  • a plurality of (preferably 2-8, 2-6 or 2-4) cooling water outlets of the heat removal pipes are combined into a cooling water outlet set in the heat removal section Tube.
  • the plurality of heat evacuation 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 is used to transport the cooling water from each heat extraction pipe to the outside world. Cooling water (generally also containing steam) after heating.
  • the heat removal pipe (referred to as the heat removal branch pipe) here can be a conventional heat removal pipe, a special-shaped heat removal pipe or any combination thereof, which is not particularly limited.
  • FIG 6 and 7 are schematic diagrams of the arrangement of the heat extraction pipe headers 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 corresponds to the plurality of heat removal branch pipes (generally referred to as the The ratio of the sum of the cross-sectional areas of the cooling water inlets or cooling water outlets of the plurality of heat withdrawal branch pipes is 0.5-1, preferably 0.55-0.95, more preferably 0.6-0.9.
  • the proportion of the heat-extraction branch pipes in the total number of the heat-extraction pipes is generally 66% or less, preferably 50% or less, and still more preferably 33% or less.
  • the outer diameters of the straight pipes are each independently 80-180 mm, preferably 90-170 mm.
  • the inner diameters of the straight pipes are each independently 60-150 mm, preferably 70-140 mm.
  • the lengths of the straight pipes are each independently 4-13m, preferably 5-12.0m.
  • the distance between two adjacent straight pipes on each of the heat extraction pipes is 100-700 mm, preferably 150-300 mm.
  • the length H of the heat removal section is 4-13m (preferably 5-12m).
  • L1/S1 is 1.0-2.5m -1 (excluding the numerical endpoint 2.5), preferably 1.4-2.2m -1 . This represents the operating state of the fluidized bed reactor at lower loads.
  • L1/S1 when the full-load hourly propylene processing capacity of the fluidized bed reactor is 200-370 kg propylene/m 2 cross-section A, L1/S1 is 1.8-4.6 m -1 , preferably 2.0-4.1m -1 . This represents the operating state of the fluidized bed reactor at intermediate load.
  • L1/S1 is 2.5-6.0 m -1 , It is preferably 2.9-5.3 m -1 . This represents the operating state of the fluidized bed reactor at higher loads and is the most preferred operating state of the present invention.
  • a fluidized bed reactor includes a sealing head, a dilute phase zone, a heat withdrawal section, a pre-reaction section and a cone in sequence from top to bottom, wherein the heat withdrawal pipe group described in any one of the preceding embodiments of the present specification is arranged in the heat withdrawal section.
  • the present invention also relates to a method for producing unsaturated nitrile, particularly a method for producing acrylonitrile.
  • the manufacturing method includes the step of ammoxidizing an olefin (eg, propylene) to produce an unsaturated nitrile (eg, acrylonitrile) in a fluidized bed reactor as described in any of the preceding embodiments of the present specification.
  • an olefin eg, propylene
  • the present invention also relates to a method for increasing the reaction load of a fluidized bed reactor.
  • the initial reaction load of the transport fluidized bed reactor its full load per hour propylene processing capacity is 140-290 kg propylene/m 2
  • the cross section A (excluding the numerical endpoint 290), at this time the fluidized bed
  • the initial value of L1/S1 for the bed reactor was 1.0-2.5 m -1 (excluding the numerical endpoint of 2.5).
  • the method includes increasing the full-load propylene throughput of the fluidized bed reactor from the initial reaction load to 290-445 kg propylene per hour/m 2 of the cross section A, and in order to accommodate This increased reaction load, to ensure that the reaction can be smoothly allowed, needs to increase the L1/S1 from the initial value to 2.5-6.0 m -1 , preferably to 2.9-5.3 m -1 .
  • 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 load of the fluidized-bed reactor is increased according to the method for increasing the load according to any one of the preceding embodiments of the present specification.
  • the ammoxidation reaction can be performed in any manner and any method conventionally known in the art, such information is known to those skilled in the art, and details are not repeated herein.
  • the operating conditions of the ammoxidation reaction for example, the molar ratio of propylene/ammonia/air (in terms of molecular oxygen) is 1:1.1-1.3:1.8-2.0, and the reaction temperature is 420-440 °C, the reaction pressure (gauge pressure) is 0.03-0.14MPa, and the weight hourly space velocity of the catalyst is 0.06-0.15h -1 .
  • Cc3out the number of moles of carbon (mol) contained in C3 in the reactor inlet gas.
  • the pressure pulsation intensity of the fluidized bed exhibits a "high frequency low amplitude" characteristic as shown in Figure 5, the fluidization quality can be evaluated as good.
  • the pressure pulsation intensity of the fluidized bed is similar to that in FIG. 5 .
  • the heat-evacuating pipes without a clear arrangement are conventional heat-evacuating pipes.
  • 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 heat pipes are arranged as shown in Figure 4A, the number of straight pipes per unit area of the cross section at the center point of the heat removal section is 7.6/m 2 , the outer diameter of the heat removal pipes is 89mm, and L1/S1 is 2.1/m.
  • the full-load propylene processing capacity at this time is 227kg propylene/h/m 2
  • the cross section A the reaction temperature is 430°C, the reaction pressure is 0.04Mpa, propylene: ammonia: air Under the condition of 1:1.2:9.6, the reaction can run stably for a long time (for example, 10000h), and the heat removal per hour is 1.24t4.5MPa saturated steam/m 2 .
  • 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. There are a total of 572 straight pipes with the same height, which are divided into 56 heat removal pipes, of which 36 are withdrawn.
  • the heat pipes are arranged as shown in Figure 4A.
  • the number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 9.0/m 2 , and each group consists of 6, 10, and 12 heat removal pipe straight pipes connected by straight pipes.
  • the outer diameter of the heat removal pipe is 140mm, and the L1/S1 is 4.0.
  • the reaction can remove the heat of 1.98t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).
  • 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 heat pipes are arranged as shown in Figure 4A.
  • the number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 11.5/m 2 , and each group consists of 6, 10, and 12 heat removal pipe straight pipes connected by straight pipes.
  • the outer diameter of the heat removal pipe is 114mm, and the L1/S1 is 4.1.
  • the reaction can remove the heat of 2.01t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).
  • 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 heat pipes are arranged as shown in Figure 4B.
  • the number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 9.18/m 2 , and each group consists of 6, 10, and 12 heat removal pipe straight pipes connected by straight pipes.
  • the outer diameter of the heat removal pipe is 114mm, and the L1/S1 is 3.3.
  • the reaction can remove the heat of 1.98t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).
  • 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 heat pipes are arranged as shown in Figure 4A.
  • the number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 11.5/m 2 , and each group consists of 6, 10, and 12 heat removal pipe straight pipes connected by straight pipes.
  • the outer diameter of the heat removal pipe is 140mm, and the L1/S1 is 5.1.
  • the reaction can remove the heat of 2.40t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).
  • 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. There are a total of 584 straight pipes with the same height, which are divided into 56 heat removal pipes, of which 32 are withdrawn.
  • the heat pipes are arranged as shown in Figure 4C.
  • the number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 9.18/m 2 , and each group consists of 6, 10, and 12 heat removal pipe straight pipes connected by straight pipes.
  • the outer diameter of the heat removal pipe is 140mm, and the L1/S1 is 4.04/m.
  • the reaction can remove the heat of 1.93t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).
  • 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 heat pipes are arranged in the way shown in Figure 4D.
  • the number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 9.18/m 2 , and each group consists of 6, 10, and 12 heat removal pipes.
  • the outer diameter of the heat removal pipe is 140mm, and the L1/S1 is 4.04/m.
  • the reaction can remove heat for a long time (for example, 10000h) per hour to 1.94t4.5MPa steam/m 2 .
  • 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. There are a total of 584 straight pipes with the same height, which are divided into 56 heat removal pipes, of which 48 are withdrawn.
  • the heat pipes are arranged as shown in Figure 4A.
  • the number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 9.18/m 2 , and each group consists of 6, 10, and 12 heat removal pipes.
  • the outer diameter of the heat removal pipe is 140mm, and the L1/S1 is 4.04.
  • the reaction can remove the heat of 1.98t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).
  • 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 full-load propylene processing capacity at this time is 349kg propylene/m 2 /h
  • the cross section A the reaction temperature is 430°C
  • the reaction pressure is 0.04Mpa
  • the heat removal tube group cannot stably control the reaction temperature. Due to the insufficient number of heat removal tubes, the long-term stable operation of the device cannot be satisfied.
  • 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. There are a total of 584 straight pipes with the same height, which are divided into 56 heat removal pipes.
  • Figure 2 For the arrangement of heat removal pipe groups, the number of straight pipes per unit area of the cross section at the center point of the heat removal section is 9.18/m 2 . , the outer diameter of the heat removal pipe is 140mm, and the L1/S1 is 4.04/m.
  • the full-load propylene processing capacity at this time is 349kg propylene/m 2 /h
  • the cross section A the reaction temperature is 430°C
  • the reaction pressure is 0.04Mpa
  • the heat removal is 1.98t steam/m 2 .
  • the device can meet the normal operation, it cannot meet the maintenance and repair of the internal components when the device is stopped.
  • 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 number of straight pipes per unit area of the cross-section at the center point of the heat removal section is 8.37/m 2
  • each group consists of 6, 10, and 12 heat removal pipe straight pipes connected in series by straight pipe connectors
  • the outer diameter of the heat removal pipe is 89mm, and the L1/S1 is 2.34.
  • the reaction can remove the heat for a long time (for example, 10000h) per hour to 1.88t 4.5MPa steam/m 2 .
  • the conversion of propylene is reduced, the yield of the reaction product is reduced, and thus the reaction exotherm is reduced.
  • 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 reaction can remove the heat of 1.98t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).
  • the fluidized bed reactor has a diameter of 9 meters and is filled with 180 tons of SANC series acrylonitrile catalyst of Sinopec Shanghai Petrochemical Research Institute.
  • Each group consists of 6, 10, and 12 straight pipes of heat removal pipes connected in series through straight pipe connectors.
  • the outer diameter of the heat removal pipes is 140mm, and the L1/S1 is 5.1.
  • the ratio of the cross-sectional area of the inlet header to the sum of the cross-sectional area of the heat removal branch is 0.83, and the ratio of the cross-sectional area of the outlet header to the sum of the cross-sectional area of the heat removal branch is 0.83.
  • the reaction can remove the heat of 2.40t4.5MPa steam/m 2 per hour for a long time (for example, 10000h).

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Abstract

一种撤热管组、利用撤热管组来提高反应负荷的方法及其在不饱和腈制造中的应用。撤热管组包括至少10个撤热管，在数量为至少1个且至多达到撤热管组中撤热管总数的88％的撤热管中，至少1个连接管件的中心轴线延长线与其他连接管件的中心轴线延长线的夹角大于0°且小于180°。

Description

一种撤热管组、反应负荷提高方法以及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。本发明进一步涉及利用该撤热管组来提高反应负荷的方法及其在不饱和腈制造中的应用。
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。
氨氧化催化剂的性能改善，容许流化床反应器(即使尺寸不变)在更大(比如提高50％)的反应负荷下操作，即原料丙烯、氨、含氧气体投料量增加50％，导致反应放热量增加50％，现有流化床反应器内虽有部分撤热管处于空闲状态，但不足于移出增加的反应热，导致反应温度失控，或者虽然在装置运行初期，勉强可以维持 反应温度的稳定，但由于缺少足够的撤热管轮换使用，随着装置运行周期的延长，撤热管表面钼垢的增加，热传导效率的下降，需更多的撤热管处于工作状态，最终的结果无空闲状态的撤热管进行切换，同样是无法维持反应温度稳定控制，因此不能满足装置长周期稳定运行的需求。另一方面，由于原料气在离开分布板/分布器时所产生的初生气泡变得更大，如此，对于现有流化床反应器，整个床层的气泡相对也变得更大，丙烯腈收率和丙烯转化率均会下降，这对装置经济性是不利的。现有的流化床反应器在撤热能力和流化效能上存在局限性，无法适应这一反应负荷提高需求。
发明内容
在本发明所涉及的丙烯腈流化床反应器中，其中各撤热管布置为彼此平行或垂直，彼此平行时间隔相同，彼此垂直时，邻近的两个撤热管直管间隔保留检修通道。常规撤热管为上连接件与下连接件以及撤热管直管在反应器截面投影在同一直线上，上连接件与下连接件成180°；异形撤热管的至少一个上连接件与下连接件成一定的角度，在沿着流体主体行进方向，流体连通的直管在反应器截面上的投影，为两条紧密相邻的直线；由于异形撤热管相对常规撤热管具有更紧密的连接，随着异形撤热管取代常规撤热管数量的增多，实现撤热能力的不断提高，也更有利于破碎大气泡。同时，撤热管之间仍有足够的空间对设备进行维护和检修。本发明基于此发现而完成，通过改变流化床反应器中撤热管的结构型式和数量，以增强流化床反应器的撤热能力和流化效能。依据氨氧化催化剂性能、反应负荷情况对常规撤热管和异形撤热管按照预定比例进行配置，实现装置高效以及长期稳定运行。
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，所述撤热管组包括至少10个(优选10至100个，更优选为20-80个)撤热管，所 述撤热管包括N个(N大于等于3，优选地，N为3至30，更优选地N为3至20)直管和用于使任意两个相邻的所述直管串联并流体连通的N-1个连接管件，
其中，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H(单位是m)，则在所述撤热段的所述长度H的整个区域内(优选在所述反应撤热段中心点上下49％H的区域内，更优选在所述反应撤热段中心点以上45％H以下38％H的区域内，更优选在所述反应撤热段中心点以上40％H以下8％H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时，获得所述撤热段的横切面(称为横切面A)，
在数量为至少1个(优选1个、2个或3个，或者占所述撤热管组中撤热管总数的至少20％、至少50％或至少65％)且至多达到所述撤热管组中撤热管总数的88％(优选75％或70％)的撤热管(称为异形撤热管)中，至少1个(优选的是，最少为2个、3个或4个，最多为该异形撤热管中连接管件总数的80％、90％或100％)连接管件(优选不包括该异形撤热管的第一个连接管件)在所述横切面A上的投影的中心轴线的延长线与至少1个其他连接管件(优选该异形撤热管上处于该连接管件的流体连通的直接上游的其他连接管件)在所述横切面A上的投影的中心轴线的延长线的夹角大于0°且小于180°(优选为30°-150°，更优选为60°-120°，更优选为约90°)。
2.前述或后述任一方面所述的撤热管组，其特征在于，设所述横切面A的面积为S1(单位是m 2)，并且设所述撤热管组的全部所述直管在所述横切面A上的横切面的外轮廓周长之和为L1(单位是m)，则L1/S1为1.0-6.0m -1(优选为2.4-5.6m -1，更优选为2.9-5.3m -1)，和/或，所述面积S1为20-700m 2(优选为35-350m 2)，和/或，所述L1为20-4200m，优选为87.5-1225m。
3.前述或后述任一方面所述的撤热管组，其特征在于，设在所述横切面A内，所述撤热管组中的全部所述直管的数量为Nt， 则所述横切面A的单位面积内的直管数量Nt/S1为4-16个/m 2(优选为5-14个/m 2，更优选为7-13个/m 2)，和/或，所述横切面A的轮廓为圆形、椭圆形或卵形，优选为圆形或基本上圆形，和/或，所述直管的横切面的内轮廓和外轮廓为圆形、椭圆形或卵形，优选为圆形或基本上圆形。
4.前述或后述任一方面所述的撤热管组，其特征在于，所述撤热管组能够回收1-10MPa的饱和蒸汽(优选2-8MPa的饱和蒸汽，更优选3-5MPa的饱和蒸汽)，和/或，在按照回收4.5MPa饱和蒸汽进行评价时，所述撤热管组的撤热能力为0.5-3.0t饱和蒸汽/单位截面积(m 2)/小时，优选1.0-2.8t饱和蒸汽/单位截面积(m 2)/小时，更优选1.2-2.4t饱和蒸汽/单位截面积(m 2)/小时，其中所述单位截面积指的是所述横切面A的单位面积。
5.前述或后述任一方面所述的撤热管组，其特征在于，在所述撤热管组中除了所述异形撤热管之外的撤热管中，任意一个连接管件在所述横切面A上的投影的中心轴线的延长线与该撤热管上处于该连接管件的流体连通的直接上游或直接下游的其他连接管件在所述横切面A上的投影的中心轴线的延长线的夹角为180°，和/或，所述撤热管包括冷却水入口，并且多个(优选为2-8个、2-6个或2-4个)所述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，所述撤热管包括冷却水出口，并且多个(优选为2-8个、2-6个或2-4个)所述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。
6.前述或后述任一方面所述的撤热管组，其特征在于，所述直管的外径各自独立地为80-180mm，优选90-170mm，和/或，所述直管的内径各自独立地为60-150mm，优选70-140mm，和/或，所述直管的长度各自独立地为4-13m，优选5-12.0m，和/或，每个所述撤热管上相邻两个直管之间的间距为100-700mm，优选150-300mm，和/或，所述撤热段的长度H为4-13m(优选5-12m)。
7.前述或后述任一方面所述的撤热管组，其特征在于，
(1)当所述流化床反应器的满负荷每小时丙烯处理量为140-290kg丙烯/m 2所述横切面A(不包括数值端点290)时，L1/S1为1.0-2.5m -1(不包括数值端点2.5)，优选为1.4-2.2m -1，或者
(2)当所述流化床反应器的满负荷每小时丙烯处理量为200-370kg丙烯/m 2横切面A时，L1/S1为1.8-4.6m -1，优选为2.0-4.1m -1，或者
(3)当所述流化床反应器的满负荷每小时丙烯处理量为290-445kg丙烯/m 2所述横切面A时，L1/S1为2.5-6.0m -1，优选为2.9-5.3m -1。
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。
9.一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。
10.一种流化床反应器的负荷提高方法，其中所述流化床反应器的满负荷每小时丙烯处理量为140-290kg丙烯/m 2所述横切面A(不包括数值端点290)，并且L1/S1为1.0-2.5m -1(不包括数值端点2.5)，该负荷提高方法包括将所述流化床反应器的满负荷每小时丙烯处理量提高至290-445kg丙烯/m 2所述横切面A的同时，将所述L1/S1增加至2.5-6.0m -1，优选增加至2.9-5.3m -1。
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负荷提高方法提高所述流化床反应器的负荷。
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0.06-0.15h -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是本发明的流化床反应撤热管组的俯视示意图。
图4A-4D是本发明的撤热管组的撤热管的布置示意图。
图5是压力脉动强度图。
图6和7是本发明的撤热管集管的布置示意图。
附图标记说明：
1：流化床反应器的器壁
2：撤热管
3：撤热管的冷却水入口
4：撤热管的冷却水出口
5：撤热管的下连接管件
6：撤热管的上连接管件
7：含氧气体分布板
8：丙烯氨分布器
9：高效旋风分离器
技术效果
根据本发明的撤热管组和流化床反应器，可以提高装置目标产物的生产能力，充分满足反应负荷提高的需求，降低装置运行成本。
根据本发明的撤热管组，实现更紧密排布，即在反应器横截面积内设更多的直管，从而增强撤热能力。
根据本发明的撤热管组和流化床反应器，可以加快流化床内流型的改变，提高传质效率。
根据本发明的撤热管组和流化床反应器，可以有效地抑制气泡的生长，从而达到提高原料气转化率，增加目标反应产物收率的目 的。
根据本发明的撤热管组和流化床反应器，可以降低气固相的返混程度，减少深度氧化产物的生成。
根据本发明的撤热管组和流化床反应器，可以提高传热效率，延长装置运行周期。
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，所述撤热管组包括至少10个(优选10至100个，更优选为20-80个)撤热管。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。优选的是，所述撤热管包括N个(N大于等于3，优选地，N为3至30，更优选地N为3至20)直管和用于使任意两个相邻的所述直管串联并流体连通的N-1个连接管件。具体如图3所示，每1个撤热管2包括：冷却水入口3、冷却水出口4、至少3个相邻的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。如图4所示，当连通任意两个直管的连接管件位于直管的下方(在后文中，有时简称为“下连接管件5”)时，则与之相邻的另一个连接管件则位于直管的上方(在后文中，有时简称为“下连接管件6”)。
在本说明书中，将一个撤热管中距离冷却水入口最近的那个直管称为第一个连接管件。另外，按照冷却水的流动方向，在一个撤热管中，各个直管表现出上下游的位置关系。本发明将相邻且处于上游的位置关系称为直接上游，将相邻且处于下游的位置关系称为直接下游。
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。为此，为了进一步改善流化情况以及装置高生产能力的需求，现有技术的撤热管组存在不能满足装置正常运行的可能。
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H(单位是m)，则在所述撤热段的所述长度H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(称为横切面A)。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％H的区域内，更优选在所述反应撤热段中心点以上45％H以下38％H的区域内，更优选在所述反应撤热段中心点以上40％H以下8％H的区域内。
根据本发明的一个实施方式，所述撤热管组包括异形撤热管。在此，在所述撤热管组中，所述异形撤热管的数量为至少1个，优选1个、2个或3个，或者占所述撤热管组中撤热管总数的至少20％、至少50％或至少65％。另外，从本发明技术效果最优异实现的角度出发，所述异形撤热管的数量至多达到所述撤热管组中撤热管总数的88％，优选75％或70％。理论上，为维持反应径向温度的一致性，希望工作中的撤热直管在反应器截面上是均匀分布的，而事实上，由于原料气投料量的变化，反应热也是随着变化，对于已在反应器床层内固定了的撤热直管，其处于工作状态的撤热直管不能做到完全均布，但是希望尽可能做到均匀分布，使得反应径向温度差尽量小，比如在3℃以内。对于化学反应其所放出的热量是可以预估的，所需的撤热直管也是可以提前测算的，由于异形撤热管所处区域撤热能力大幅度增加，处于工作状态相邻的异形撤热管之间的距离会增加，虽然流化床传热效率高，但导致存在这两个异形撤热管之间的反应热移出不及时的风险。如果所述撤热管组中的全部(100％)撤热管都是异形撤热管，则本发明的预期技术效果将无法有效实现。
根据本发明的一个实施方式，所谓异形撤热管，指的是其所包含的至少1个连接管件(称为特殊连接管件)在所述横切面A上的投影的中心轴线的延长线与至少1个其他连接管件在所述横切面A上的投影的中心轴线的延长线的夹角(夹角A)大于0°且小于180°的撤热管。所述夹角A优选为30°-150°，更优选为60°-120°。从本发明技术效果最优异实现的角度出发，所述夹角A最优选为约90°，实现撤热直管的紧密排布。另外，作为所述特殊连接管件在一个异形撤热管中的数量，优选最少为2个、3个或4个，最多为该异形撤热管中连接管件总数的80％、90％或100％。从本发明技术效果最优异实现的角度出发，所述特殊连接管件的数量优选为该异形撤热管中连接管件总数的100％，便于各撤热管布置为彼此平行且间隔相同，同时保证装置足够的检修通道。
根据本发明的一个实施方式，作为所述至少1个其他连接管件，优选该异形撤热管上处于该连接管件的流体连通的直接上游的其他连接管件。另外，考虑到第一个连接管件不存在直接上游，因此这里所述的连接管件一般不包括该异形撤热管的第一个连接管件。虽然如此，所述第一个连接管件在所述横切面A上的投影的中心轴线的延长线与所述冷却水入口在所述横切面A上的投影的中心轴线的延长线的夹角(夹角A1)可以是任意数值，比如是30°-180°、60°-180°、90°或180°。与前述同样道理，所述夹角A1同样优选90°。
具体而言，在所述横截面上的投影中，同一个撤热管2中的直管和连接管件比如可以按照图4A-4D所示的布置方式来布置。
根据本发明的一个实施方式，撤热管组中的撤热管2的直管的横切面外轮廓基本上为圆形，其外轮廓周长为3.14×D。在此，D为所述直管外轮廓的直径。因此，在如图3所示的所述撤热段的横切面内，所述撤热管组的全部直管的横切面的外轮廓周长之和L1即为所述撤热段的横切面内全部直管的外轮廓周长的总和。
根据本发明的一个实施方式，设所述横切面A的面积为S1(单 位是m 2)，并且设所述撤热管组的全部所述直管在所述横切面A上的横切面的外轮廓周长之和为L1(单位是m)，则L1/S1为1.0-6.0m -1(优选为2.4-5.6m -1，更优选为2.9-5.3m -1)。在此，L1/S1代表全部撤热管(或直管)在所述横切面A上的布置密度，其存在对于本发明的技术效果实现而言最佳的范围。在L1/S1布置密度低于1.0时，装置运行反应负荷低，对企业而言，生产成本高经济性差，在L1/S1布置密度高于6.0时，可以在反应高负荷运行，满足更多反应热移出的需求，反应器内异形撤热管数量会增加，在操作过程中不利于反应温度的稳定，或者挤压维检修的空间。
根据本发明的一个实施方式，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，所述撤热管组包括至少1个(优选10至100个，更优选为20-80个)撤热管，所述撤热管包括N个(N大于等于3，优选地，N为3至30，更优选地N为3至20)直管和用于使任意两个相邻的所述直管串联并流体连通的N-1个连接管件，其中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H(单位是m)，则在所述撤热段的所述长度H的整个区域内，(优选在所述反应撤热段中心点上下49％H的区域内更优选在所述反应撤热段中心点以上45％H以下38％H的区域内，更优选在所述反应撤热段中心点以上40％H以下8％H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时，设所述撤热段的横切面的面积为S1(单位是m 2)，在所述撤热管中，至少1个连接管件在所述横切面上的投影的中心轴线的延长线与至少1个其他连接管件在所述横切面上的投影的中心轴线的延长线的夹角大于0°且小于180°，(优选为30°-150°，更优选为60°-120°，更优选为90°)，并且在所述横切面内，所述撤热管组的全部直管的横切面的外轮廓周长之和为L1(单位是m)，则L1/S1为1.0-6.0m -1(优选为2.0-4.0m -1，更优选为2.5-3.5m -1)。
根据本发明的一个实施方式，所述面积S1为20-700m 2(优选为35-350m 2)。
根据本发明的一个实施方式，所述L1为20-4200m，优选为87.5-1225m。
根据本发明的一个实施方式，设在所述横切面A内，所述撤热管组中的全部所述直管的数量为Nt，则所述横切面A的单位面积内的直管数量Nt/S1为4-16个/m 2(优选为5-14个/m 2，更优选为7-13个/m 2)。在此，Nt/S1同样代表撤热管(或直管)在所述横切面A上的布置密度，其存在对于本发明的技术效果实现而言最佳的范围。在Nt/S1布置密度低于4时，对流化床而言，不利于破碎气泡，导致更多的原料气未参与反应就随气体带出反应器，影响反应结果，在Nt/S1布置密度高于16时，同样是可以满足反应高负荷运行，但是存在异形撤热管增加导致操作过程中反应温度的不稳定，以及挤压维检修空间的风险。
根据本发明的一个实施方式，所述横切面A的轮廓为圆形、椭圆形或卵形，优选为圆形或基本上圆形。
根据本发明的一个实施方式，所述直管的横切面的内轮廓和外轮廓为圆形、椭圆形或卵形，优选为圆形或基本上圆形。
根据本发明的一个实施方式，所述撤热管组能够回收1-10MPa的饱和蒸汽，优选2-8MPa的饱和蒸汽，更优选3-5MPa的饱和蒸汽。特别地，在按照回收4.5MPa饱和蒸汽进行评价时，所述撤热管组的撤热能力为0.5-3.0t饱和蒸汽/单位截面积(m 2)/小时，优选1.0-2.8t饱和蒸汽/单位截面积(m 2)/小时，更优选1.2-2.4t饱和蒸汽/单位截面积(m 2)/小时，其中所述单位截面积指的是所述横切面A的单位面积。与现有技术相比，本发明的撤热管组能够回收更多的饱和蒸汽，由此显示出更为强大的撤热能力，满足反应高负荷的需求。
根据本发明的一个实施方式，所述撤热管组还包括常规撤热管，所述常规撤热管和所述异形撤热管共同构成了所述撤热管组。在此，在一个常规撤热管中，任意一个连接管件在所述横切面A上的投影的中心轴线的延长线与该撤热管上处于该连接管件的流体 连通的直接上游或直接下游的其他连接管件在所述横切面A上的投影的中心轴线的延长线的夹角为180°。简单来说，作为所述常规撤热管，全部的直管处于同一个平面中。
在本说明书的上下文中，在没有明确指出的情况下，撤热管在其含义中涵盖异形撤热管和常规撤热管。
根据本发明的一个实施方式，多个(优选为2-8个、2-6个或2-4个)所述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，所述多个撤热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撤热管供应冷却水。这里的撤热管(称为撤热支管)可以是常规撤热管、异形撤热管或其任意组合，并没有特别的限定。
根据本发明的一个实施方式，多个(优选为2-8个、2-6个或2-4个)所述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，所述多个撤热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撤热管向外界输送撤热之后的冷却水(一般还包含蒸汽)。这里的撤热管(称为撤热支管)可以是常规撤热管、异形撤热管或其任意组合，并没有特别的限定。
图6和7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撤热支管(一般以所述多个撤热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。另外，所述撤热支管在所述撤热管的总数中所占的比例一般为66％以下，优选为50％以下，还更优选为33％以下。
根据本发明的一个实施方式，所述直管的外径各自独立地为 80-180mm，优选90-170mm。
根据本发明的一个实施方式，所述直管的内径各自独立地为60-150mm，优选70-140mm。
根据本发明的一个实施方式，所述直管的长度各自独立地为4-13m，优选5-12.0m。
根据本发明的一个实施方式，每个所述撤热管上相邻两个直管之间的间距为100-700mm，优选150-300mm。
根据本发明的一个实施方式，所述撤热段的长度H为4-13m(优选5-12m)。
根据本发明的一个实施方式，当所述流化床反应器的满负荷每小时丙烯处理量为140-290kg丙烯/m 2所述横切面A(不包括数值端点290)时，L1/S1为1.0-2.5m -1(不包括数值端点2.5)，优选为1.4-2.2m -1。这代表了流化床反应器在较低负荷下的操作状态。
根据本发明的一个实施方式，当所述流化床反应器的满负荷每小时丙烯处理量为200-370kg丙烯/m 2横切面A时，L1/S1为1.8-4.6m -1，优选为2.0-4.1m -1。这代表了流化床反应器在中间负荷下的操作状态。
根据本发明的一个实施方式，当所述流化床反应器的满负荷每小时丙烯处理量为290-445kg丙烯/m 2所述横切面A时，L1/S1为2.5-6.0m -1，优选为2.9-5.3m -1。这代表了流化床反应器在较高负荷下的操作状态，是本发明最为优选的操作状态。
根据本发明的一个实施方式，还涉及一种流化床反应器。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本说明书如前任一实施方式所述的撤热管组。
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，特别是丙烯腈的制造方法。该制造方法包括在本说明书如前任一实施方式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。
根据本发明的一个实施方式，还涉及一种流化床反应器的反应 负荷提高方法。在此，作为输送流化床反应器的初始反应负荷，其满负荷每小时丙烯处理量为140-290kg丙烯/m 2所述横切面A(不包括数值端点290)，此时所述流化床反应器的L1/S1初始值为1.0-2.5m -1(不包括数值端点2.5)。为了实现反应负荷提高，所述方法包括将所述流化床反应器的满负荷丙烯处理量从所述初始反应负荷提高至每小时290-445kg丙烯/m 2所述横切面A，并且为了适应该提高的反应负荷以确保反应能够平稳允许，需要将所述L1/S1从所述初始值增加至2.5-6.0m -1，优选增加至2.9-5.3m -1。
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，其中按照本说明书如前任一实施方式所述的负荷提高方法提高所述流化床反应器的负荷。
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0.06-0.15h -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)。
本领域已知的是，如果流化床的压力脉动强度表现为如图5所示的“高频低幅”特性，则流化质量可以评价为良好。在以下的全部实施例中，流化床的压力脉动强度均与图5相似。
在以下的实施例和比较例中，没有明确排布方式的撤热管是常规撤热管。
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480个，分为44个撤热管，其中12个撤热管采用图4A的排布方式，撤热段中心点处的横切面单位面积内的直管数量为7.6个/m 2，撤热管外径为89mm，L1/S1为2.1/m。
在丙烯进料量为7700NM 3/h，此时的满负荷丙烯处理量为227kg丙烯/h/m 2所述横切面A，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，反应能够长时间(比如10000h)稳定运行，每小时撤热量为1.24t4.5MPa饱和蒸汽/m 2。
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572个，分为56个撤热管，其中36个撤热管采用图4A所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为9.0个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为140mm，L1/S1为4.0。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为1.98t4.5MPa蒸汽/m 2。
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732个，分为70个撤热管，其中42个撤热管采用图4A所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为11.5个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为114mm，L1/S1为4.1。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为2.01t4.5MPa蒸汽/m 2。
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584个，分为58个撤热管，其中36个撤热管采用图4B所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为9.18个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为114mm，L1/S1为3.3。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为1.98t4.5MPa蒸汽/m 2。
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，分为72个撤热管，其中52个撤热管采用图4A所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为11.5个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为140mm，L1/S1为5.1。
在丙烯进料量为14400NM 3/h，此时的满负荷丙烯处理量为425kg丙烯/m 2/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为2.40t4.5MPa蒸汽/m 2。
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584个，分为56个撤热管，其中32个撤热管采用图4C所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为9.18个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为140mm，L1/S1为4.04/m。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为1.93t4.5MPa蒸汽/m 2。
实施例7
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，分为56个撤热管，其中32个撤热管采用图4D所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为9.18个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为140mm，L1/S1为4.04/m。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为1.94t4.5MPa蒸汽/m 2。
实施例8
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，分为56个撤热管，其中48个撤热管采用图4A所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为9.18个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为140mm，L1/S1为4.04。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为1.98t4.5MPa蒸汽/m 2。
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380个，分为36组，采用图2的撤热管组排布方式，撤热段中心点处横切面单位面积内的直管数量为6.0个/m 2，撤热管外径为89mm，L1/S1为1.67/m。
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/小时所述横切面A，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，在装置运行过程中，撤热管组无法稳定控制反应温度，由于撤热管数量不足，不能满足装置长期稳定运行。
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56个撤热管，采用图2撤热管组排布方式，撤热段中心点处横切面单位面积内的直管数量为9.18个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为140mm，L1/S1为4.04/m。
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/小时所述横切面A，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，撤热量为1.98t蒸汽/m 2。
装置虽然能满足正常运行，但是无法满足装置停车时对内构件的维检修。
比较例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532个，分为46个撤热管，撤热管全部采用图4A所示的排布方式，撤热段中心点处横切面单位面积内的直管数量为8.37个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为89mm，L1/S1为2.34。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为1.88t 4.5MPa蒸汽/m 2。与实施例2相比，由于流化质量变差，导致丙烯转化率降低，反应产物收率降低，因此反应放热减少。
实施例8
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，分为70个撤热管，有4组是由3个撤热管组并联连接，撤热管入口集管外径为140mm,撤热管出口集管外径为150mm,撤热段中心点处横切面单位面积内的直管数量为11.5个/m 2，每个撤热管由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为89mm，L1/S1为3.2，入口集管截面积与撤热支管横截面积之和比值为0.82，出口集管截面积与撤热支管横截面积之和比值为0.95。
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/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为1.98t4.5MPa蒸汽/m 2。
实施例9
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，分为70个撤热管，其中有10组是由2个撤热管组并联连接，撤热管入口集管外径为180mm,撤热管出口集管外径为180mm,撤热段中心点处横切面单位面积内的直管数量为11.5个/m 2，每组由6、10、12个撤热管直管通过直管连接件串联而成，撤热管外径为140mm，L1/S1为5.1。入口集管截面积与撤热支管横截面积之和比值为0.83，出口集管截面积与撤热支管横截面积之和比值为0.83。
在丙烯进料量为14400NM 3/h，此时的满负荷丙烯处理量为425kg丙烯/m 2/小时所述横切面A，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，反应能够长时间(比如10000h)每小时撤热量为2.40t4.5MPa蒸汽/m 2。

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，所述撤热管组包括至少10个(优选10至100个，更优选为20-80个)撤热管，所述撤热管包括N个(N大于等于3，优选地，N为3至30，更优选地N为3至20)直管和用于使任意两个相邻的所述直管串联并流体连通的N-1个连接管件，
    其中，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H(单位是m)，则在所述撤热段的所述长度H的整个区域内(优选在所述反应撤热段中心点上下49％H的区域内，更优选在所述反应撤热段中心点以上45％H以下38％H的区域内，更优选在所述反应撤热段中心点以上40％H以下8％H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时，获得所述撤热段的横切面(称为横切面A)，
    在数量为至少1个(优选1个、2个或3个，或者占所述撤热管组中撤热管总数的至少20％、至少50％或至少65％)且至多达到所述撤热管组中撤热管总数的88％(优选75％或70％)的撤热管(称为异形撤热管)中，至少1个(优选的是，最少为2个、3个或4个，最多为该异形撤热管中连接管件总数的80％、90％或100％)连接管件(优选不包括该异形撤热管的第一个连接管件)在所述横切面A上的投影的中心轴线的延长线与至少1个其他连接管件(优选该异形撤热管上处于该连接管件的流体连通的直接上游的其他连接管件)在所述横切面A上的投影的中心轴线的延长线的夹角大于0°且小于180°(优选为30°-150°，更优选为60°-120°，更优选为约90°)。
  2. 权利要求1所述的撤热管组，其特征在于，设所述横切面A的面积为S1(单位是m 2)，并且设所述撤热管组的全部所述直管在所述横切面A上的横切面的外轮廓周长之和为L1(单位是m)， 则L1/S1为1.0-6.0m -1(优选为2.4-5.6m -1，更优选为2.9-5.3m -1)，和/或，所述面积S1为20-700m 2(优选为35-350m 2)，和/或，所述L1为20-4200m，优选为87.5-1225m。
  3. 权利要求1所述的撤热管组，其特征在于，设在所述横切面A内，所述撤热管组中的全部所述直管的数量为Nt，则所述横切面A的单位面积内的直管数量Nt/S1为4-16个/m 2(优选为5-14个/m 2，更优选为7-13个/m 2)，和/或，所述横切面A的轮廓为圆形、椭圆形或卵形，优选为圆形或基本上圆形，和/或，所述直管的横切面的内轮廓和外轮廓为圆形、椭圆形或卵形，优选为圆形或基本上圆形。
  4. 权利要求1所述的撤热管组，其特征在于，所述撤热管组能够回收1-10MPa的饱和蒸汽(优选2-8MPa的饱和蒸汽，更优选3-5MPa的饱和蒸汽)，和/或，在按照回收4.5MPa饱和蒸汽进行评价时，所述撤热管组的撤热能力为0.5-3.0t饱和蒸汽/单位截面积(m 2)/小时，优选1.0-2.8t饱和蒸汽/单位截面积(m 2)/小时，更优选1.2-2.4t饱和蒸汽/单位截面积(m 2)/小时，其中所述单位截面积指的是所述横切面A的单位面积。
  5. 权利要求1所述的撤热管组，其特征在于，在所述撤热管组中除了所述异形撤热管之外的撤热管中，任意一个连接管件在所述横切面A上的投影的中心轴线的延长线与该撤热管上处于该连接管件的流体连通的直接上游或直接下游的其他连接管件在所述横切面A上的投影的中心轴线的延长线的夹角为180°，和/或，所述撤热管包括冷却水入口，并且多个(优选为2-8个、2-6个或2-4个)所述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，所述撤热管包括冷却水出口，并且多个(优选为2-8个、2-6个或2-4个)所述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。
  6. 权利要求1所述的撤热管组，其特征在于，所述直管的外径各自独立地为80-180mm，优选90-170mm，和/或，所述直管的 内径各自独立地为60-150mm，优选70-140mm，和/或，所述直管的长度各自独立地为4-13m，优选5-12.0m，和/或，每个所述撤热管上相邻两个直管之间的间距为100-700mm，优选150-300mm，和/或，所述撤热段的长度H为4-13m(优选5-12m)。
  7. 权利要求1所述的撤热管组，其特征在于，
    (1)当所述流化床反应器的满负荷每小时丙烯处理量为140-290kg丙烯/m 2所述横切面A(不包括数值端点290)时，L1/S1为1.0-2.5m -1(不包括数值端点2.5)，优选为1.4-2.2m -1，或者
    (2)当所述流化床反应器的满负荷每小时丙烯处理量为200-370kg丙烯/m 2横切面A时，L1/S1为1.8-4.6m -1，优选为2.0-4.1m -1，或者
    (3)当所述流化床反应器的满负荷每小时丙烯处理量为290-445kg丙烯/m 2所述横切面A时，L1/S1为2.5-6.0m -1，优选为2.9-5.3m -1。
  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. 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。
  10. 一种流化床反应器的负荷提高方法，其中所述流化床反应器的满负荷每小时丙烯处理量为140-290kg丙烯/m 2所述横切面A(不包括数值端点290)，并且L1/S1为1.0-2.5m -1(不包括数值端点2.5)，该负荷提高方法包括将所述流化床反应器的满负荷每小时丙烯处理量提高至290-445kg丙烯/m 2所述横切面A的同时，将所述L1/S1增加至2.5-6.0m -1，优选增加至2.9-5.3m -1。
  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10所述的负荷提高方法提高所述流化床反 应器的负荷。
  12. 权利要求9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0.06-0.15h -1。
PCT/CN2022/085766 2021-04-09 2022-04-08 一种撤热管组、反应负荷提高方法以及不饱和腈的制造方法 WO2022214067A1 (zh)

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