CN110770520A - For C3-C5Shell-and-tube heat exchanger in a process for dehydrogenation of hydrocarbons (variants) - Google Patents
For C3-C5Shell-and-tube heat exchanger in a process for dehydrogenation of hydrocarbons (variants) Download PDFInfo
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- CN110770520A CN110770520A CN201880038577.8A CN201880038577A CN110770520A CN 110770520 A CN110770520 A CN 110770520A CN 201880038577 A CN201880038577 A CN 201880038577A CN 110770520 A CN110770520 A CN 110770520A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
- F28D7/16—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged in parallel spaced relation
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Abstract
The invention relates to a shell-and-tube counterflow heat exchanger for use in a heat exchanger3‑C5A process for the dehydrogenation of paraffinic hydrocarbons wherein the heat of the contact gas leaving the dehydrogenation reactor is used to heat the feed vapor, said heat exchanger comprising: a vertical cylindrical housing (1); a heat exchange tube bundle (2) having an upper tube sheet (4) and a lower tube sheet (3); a conduit (5) and a distribution chamber (6) for introducing a contact gas into the upper part of the tube side (2) of the heat exchanger (11); a collection chamber (7) and a conduit (8) for discharging cooled contact gas from a lower portion of the tube side; a conduit (9) for introducing feed vapor into the shell side of a heat exchanger (11), wherein the shell side is staged with waterThe flat transverse baffle (13) is divided into a plurality of sections; and a conduit (10) for withdrawing heated feed vapor from the shell side. The heat exchanger is characterized in that the heat exchanger (11) comprises valves (12) for supplying a portion of the feed supplied in liquid form to the heat exchange tube bundle (2) to the shell side of the heat exchange tube bundle (2) and/or to the shell side of the heat exchange tube bundle (2) divided into a plurality of sections (17), the plurality of sections (17) being defined by an upper tube sheet (4) and a lower tube sheet (3) and vertical channels (18) between the plurality of sections (17). Variations of shell and tube heat exchangers for cooling contact gases have also been proposed. The technical effect of the claimed invention is an improvement in the method for the pair C3‑C5The productivity of the equipment in which the hydrocarbons are dehydrogenated and the operating costs are reduced.
Description
Technical Field
The invention relates to the field of petrochemistry, in particular to a method for mixing C3-C5A device for dehydrogenating hydrocarbons to the corresponding main monomers for the production of synthetic rubbers and to the production of olefins and diolefins, such as polypropylene, methyl tert-butyl ether and the like.
Background
A known plant for the production of butenes by dehydrogenation of n-butane in a fluidized bed of a fine-grained chromia-alumina catalyst, in which a quenching coil (quenching coil) located in the separation zone of the reactor and heated by contact with the heat of the dehydrogenation gas is used to heat the vapours of the feedstock (I.L. Kirpichnikov, V.V. Bersenev, L.M. Popov, "set of technical schemes of the synthetic rubber industry (Album of technical schemes of the industrial rubber industry)", Khimia, Raningger, 1986, pages 8-12). However, the low heat transfer coefficient of the quenching coil used determines the large metal consumption and the complexity of the latter design, limiting its performance. Furthermore, heating the feed vapor in the quench coil in a known manner requires additional superheating of the feed vapor by flame heating the furnace feed coil in a high power furnace by burning large quantities of gaseous and/or liquid fuel before feeding the feed vapor to the reactor. At the same time, the large amount of flue gas delivered to the atmosphere from the furnace creates significant environmental problems.
The closest technical point to that proposed is a shell-and-tube counter-current heat exchanger that uses the heat of the contact gas exiting the propane dehydrogenation reactor to heat the feed vapor (patent RU 2523537, International Patent Classification (IPC): B01J8/18, C07C5/333, published 2014, 7/20 days), which comprises: a vertical cylindrical housing; a heat exchange tube bundle having an upper tube sheet and a lower tube sheet; a conduit (pipe) and distribution chamber for introducing a contact gas into an upper portion of a tube side of the heat exchanger; a collection chamber and conduit for discharging cooled contact gas from the bottom of the tube side; and a conduit for inputting feed vapor to a shell side of the heat exchanger and for outputting heated feed vapor therefrom. Well known shell and tube heat exchangers may have segmented horizontal transverse baffles in the shell side that divide the shell side along the height into multiple sections for providing multiple transverse movements of feed vapor in relation to the heat exchange tubes (a.n. planovski, v.m. ramm, s.z. kagan, "Chemical Processes and equipment (Processes and catalysts of Chemical Technology)", Moscow, Khimia,1968, page 434-428). However, at the contact gas dehydrogenation temperature of 540-. This is particularly true for large heat exchangers in large capacity plants, due to the presence of a stagnant zone (steady zone) in the shell side of such heat exchangers, particularly at the outlet of the heated feed vapor from the shell side. All this leads to a gradual decrease of the heat transfer efficiency in the heat exchanger by blocking a part of its heat transfer surface in the upper high temperature zone. At the same time, the hydraulic resistance (hydraulic resistance) to the gas flow increases, and therefore, from the viewpoint of its mechanical strength, the pressure of the shell side increases to the maximum value allowed for the heat exchanger shell (shell) due to the flow-blocking portion of the formed coke (formdcoke) to the shell side of the heat exchanger. As the temperature, pressure and residence time of the feed vapor increases, the rate of formation of the hot polymer increases. This condition leads to deterioration of the operating conditions of the main components of the dehydrogenation unit (associated with insufficient heating of the feed steam fed to the reactor), in particular to a disturbance of the thermal mode of the furnace, of the reactor for superheating of the feed steam, and of the scrubber for cooling and water washing of the contact gas (associated with an increase in the temperature of the contact gas at the outlet of the heat exchanger and therefore at the inlet of the scrubber), with consequent increase in the temperature and pressure at the inlet of the product turbocharger and therefore in the pressure in the dehydrogenation reactor. These disadvantages lead to a deterioration of the dehydrogenation process performance (leading to a reduction in the reactor feed load, a reduction in the yield of the target product and thus a reduction in the yield of the target product) and to an early process shutdown to clean the heat exchanger with the associated costs.
Also very close to the technical point proposed is a shell-and-tube counterflow heat exchanger for cooling C between the turbocharger stages of a contact gas condenser unit at high pressure with counterflow of cooling industrial water4Contact gas for hydrocarbon dehydrogenation processes (patent SU 1230154, IPC: C07C11/12, published 1999, 10/20), comprising: a vertical cylindrical housing (shell); a heat exchange tube bundle having an upper tube sheet and a lower tube sheet; a pipe and a distribution chamber for introducing cooling water into a lower portion of the tube space of the heat exchanger; a collection chamber and tube for drawing hot water from an upper portion of the tube side; and a conduit for introducing the contact gas into the shell side of the heat exchanger, divided into sections by segmented horizontal transverse baffles, and discharging cooled contact gas therefrom, wherein a line preceding the conduit for introducing the contact gas into the heat exchanger includes a valve (tap) for supplying vapor condensate and/or vapor to the shell side. In this case, the vapour condensate is obtained by condensation of the vapour. However, the use of this solution does not sufficiently prevent the turbocharger and the interstage heat exchanger at high pressure from being clogged with polymer. After 1500 hours of initial operation, the turbochargerThe take-up load was stopped while the pressure at the inlet of the compressor and correspondingly in the dehydrogenation reactor increased, which resulted in a decrease in the average butadiene yield per run (1-2%) and shutdown of the compressor. Significant plugging of the impeller and guide vanes of the compressor flow path and the shell side of the interstage heat exchanger by the polymer was observed when the compressor was turned on. Furthermore, processes involving additional streams of expensive materials in the form of steam condensate and/or steam also result in an increase in the amount of wastewater from the process and, therefore, in an increase in their disposal costs.
Disclosure of Invention
The object of the invention is to improve the performance of heat exchangers and thus to improve the performance for C3-C5Performance of the hydrocarbon dehydrogenation plant and reduced operating costs.
To solve this problem, a shell-and-tube heat exchanger is proposed, which is used in C3-C5A process for the dehydrogenation of paraffinic hydrocarbons in which the feed vapor is heated by the heat of contact gas exiting a dehydrogenation reactor in countercurrent flow, comprising: a vertical cylindrical housing 1; a heat exchange tube bundle (a bundle of heat exchange tubes)2 having an upper tube sheet 4 and a lower tube sheet 3; a pipe 5(pipe) and a distribution chamber 6 for introducing a contact gas into an upper portion of a tube side (tube side)2 of the heat exchanger 11; a collection chamber 7 and a duct 8 for discharging cooled contact gas from the lower part of the tube side; a conduit 9 for introducing feed vapor into the shell side of a heat exchanger 11, wherein the shell side is divided into a plurality of sections by segmented horizontal transverse baffles 13; and a conduit 10 for withdrawing heated feed vapor from the shell side, wherein the heat exchanger 11 comprises a valve 12 for supplying a portion of the feed supplied in liquid form to the heat exchanger 11 to the shell side of the heat exchanger tube bundle 2 and/or to the shell side of the heat exchanger tube bundle 2 divided into a plurality of sections (sectors)17, the plurality of sections 17 being defined by the upper and lower tube sheets 4, 3 and vertical passages 18 between the plurality of sections 17.
The width of the channels 18 between the plurality of sections 17 may be 0.25 to 2.0 times the diameter of the heat exchange tube.
A valve 12 for supplying a portion of the feed in liquid form to the shell side may be provided in the upper part of the shell 1 at a distance from the upper tube sheet 4 of the heat exchanger 11, wherein the distance is 15-50% of the height of the shell 1.
The heat exchange tube bundle 2 in each section may have 1-3 additional horizontal transverse baffles 14 insulating the position of the exchange tubes therebetween, wherein 1-4 spaced transverse baffles 14 are located in the upper portion of the heat exchange tube bundle 2 below the upper tube sheet 4, which have fins (flaps) 15 that may abut the edges of the additional spaced transverse baffles 14 at the outlet of the feed vapor from the heat exchange tube bundle 2, the fins being bent downwardly at an angle of 20 ° to 40 ° in the flow direction of the feed vapor.
A valve 12 for supplying a portion of the feed in liquid form to the shell side may be disposed opposite the passage 18 between the plurality of sections 17 in the flow direction of the feed vapor.
The channels 18 between the sections 17 may have an open inlet for feed vapor and an outlet closed by the walls of the shell 1.
The heat exchange tube bundle 2 may have a circular, rectangular or trapezoidal shape in horizontal section.
The plurality of segments 17 in heat exchange tube bundle 2 may have a triangular, square, rectangular or trapezoidal shape in horizontal cross-section.
The heat exchange tube bundle 2 may have an in-line (square-numbered) tube arrangement.
The tube sheet of the shell-and-tube heat exchanger may be removable.
The valve 12 for supplying the liquid feed may be equipped with a nozzle for injection and atomization of the feed.
In order to solve the above problems, there has also been proposed a shell-and-tube heat exchanger for cooling C under pressure between turbochargers of different stages in a contact gas condenser unit using a counter flow of cooling process water4A contact gas for a hydrocarbon dehydrogenation process, the heat exchanger comprising: a vertical cylindrical housing; a heat exchange tube bundle having an upper tube sheet 23 and a lower tube sheet 24; a conduit 27 and distribution chamber for introducing cooling water into the lower portion of the tube side of the heat exchanger; for discharging hot water from the upper part of the tube sideThe collection chamber and conduit 28; a conduit 21 for introducing the contact gas into the shell side of the heat exchanger, wherein the shell side is divided into a plurality of sections by segmented horizontal transverse baffles; and a conduit 26 for discharging cooled contact gas from the shell side, wherein the heat exchanger comprises a valve 19 for supplying water condensate of the dehydrogenation process to the shell side of the heat exchanger tube bundle and/or to the shell side of the heat exchanger tube bundle divided into a plurality of sections 22, the plurality of sections 22 being defined by upper and lower tube sheets 23, 24 and vertical channels 25 between the plurality of sections 22, the valve being provided on the line 20 supplying contact gas to the heat exchanger and/or in an upper portion of the heat exchanger shell.
The heat exchanger may comprise a valve 19 at the level of a conduit 21, which conduit 21 is used for introducing the contact gas into the heat exchanger.
The width of the channels 25 between the plurality of sections 22 may be 0.25-2.0 times the diameter of the heat exchange tube.
The valve 19 may be disposed opposite to the passage 25 between the plurality of sections 22 in the flow direction of the contact gas.
The channels 25 between the plurality of sections 22 may have open inlets for contacting gas and outlets closed by the walls of the housing.
The heat exchange tube bundle may have a circular, square, rectangular or trapezoidal shape in horizontal cross section.
The plurality of segments 22 in the heat exchange tube bundle may have a triangular, square, rectangular or trapezoidal shape in horizontal cross-section.
The heat exchange tube bundle may have an in-line (square-numbered) tube arrangement.
The tube sheet of the shell-and-tube heat exchanger may be removable.
The valve 19 may be equipped with a nozzle for injection and atomization of the water condensate of the dehydrogenation process.
The heat exchange tube bundle may have a circular shape in horizontal cross-section, and the number of the plurality of segments 22 in the heat exchange tube bundle may be selected according to the following relationship:
Nsegment of＝KP/9h，
Wherein N isSegment ofIs the number of multiple segments in the tube bundle;
k is a rounding factor, varying between 1.0 and 1.5;
h is the tube bundle spacing;
p is the circumference of the outer tubes in the tube bundle.
At proposed usage leave C3-C5In a heat exchanger 11 for heating feed vapor in countercurrent to contact gas of a paraffin dehydrogenation reactor, a valve 12 is provided for supplying a part of the feed in liquid form supplied to the heat exchanger to the shell side, and particularly the valve 12 is provided in the upper part of the shell 1 at a distance of 15 to 50% of the height of the shell 1 from the upper tube sheet 4, so that the temperature in the upper high temperature part of the heat exchanger 11 is lowered by evaporation of the liquid feed, thereby reducing the amount of hot polymer formed and eliminating the deposition of the hot polymer on the heat transfer surface by flushing the deposition with an atomized liquid feed stream evaporated in the high temperature part of the heat exchanger 11, which is liable to form the hot polymer.
Dividing the heat exchange tube bundle 2 into a plurality of sections 17 such that the permeation of the superheated feed vapor stream into the heat exchange tube bundle 2 is increased (particularly in large capacity heat exchangers having up to thousands of heat exchange tubes), the plurality of sections 17 being defined by upper and lower tube sheets 4, 3 and channels 18 between the plurality of sections 17, wherein the width of the channels is 0.25-2.0 times the diameter of the heat exchange tubes. The channels 18 operate as manifolds which distribute the flow of feed vapor to the various sections 17 of the heat exchange tube bundle 2 (adjacent to the channels 18), ensuring the elimination of stagnation phenomena and the operation of all the heat exchange tubes 2 of the heat exchanger 11. This prevents the hot polymer from clogging the flow features (flow part) of the heat exchanger 11, significantly increasing the heat transfer coefficient observed, and also prevents the heat exchanger shell side pressure from increasing while reducing the shell side hydraulic resistance.
In providing multiple lateral movements of feed vapor in relation to the heat exchange tubes, the following arrangement provides the ability to prevent stagnation in the shell side of the heat exchanger, particularly for high productivity heat exchangers: in each section of the heat exchange tube bundle 2 are provided one to three further spaced heat exchange tube position transverse baffles 14 and one to four spaced baffles 14 in the upper part of the heat exchange tube bundle 2 below the upper tube sheet 4, which have fins 15, which fins 15 at the outlet of the feed vapour from the heat exchange tube bundle 2 are adjacent to the edges of the spaced baffles 14 and are bent downwards in the flow direction of the feed vapour at an angle of 20 ° to 40 °. The following settings provide the conditions necessary to feed the feed in liquid form to the tubes in the central portion of the heat exchange bundle: the valve 12 for supplying a part of the feed in liquid form to the shell side is disposed opposite to the passage 18 between the plurality of sections 17 in the flow direction of the feed vapor, and an open inlet for supplying a part of the feed in liquid form into the passage 18 and an outlet closed by the wall of the housing 1 and having a width of 0.25 to 2.0 times the tube diameter. At the outlet for feed vapour from the channel 18 closed by the walls of the housing 1 there is provided a hydraulic head for the flow of feed vapour in the channel which helps to distribute the feed vapour into the plurality of sections 17 of the heat exchange tubes 2 adjacent to the channel 18. This also helps prevent stagnation in the shell side of the heat exchanger 11 for heating the feed vapor and increases the heat transfer coefficient in the heat exchanger.
Method for cooling C between turbocharger stages in contact gas condenser unit using counterflow of cooling water at high pressure4In a gas-contacting shell-and-tube heat exchanger for a hydrocarbon dehydrogenation process, clogging of a turbocharger and an interstage shell-and-tube heat exchanger due to thermal polymer deposition is significantly reduced by lowering the temperature of the contact gas stream, suppressing thermal polymerization, and flushing the flow path of thermal polymer deposits by the flow of atomized condensed water during dehydrogenation, as follows: a valve 19 is provided for supplying process water condensate to the shell side (wherein the valve is provided on a line 20 supplying contact gas to the heat exchanger and/or in the upper part of the shell at a level of the location of the tubes 21 for introducing contact gas to the heat exchanger and/or the heat exchange tube bundle 2 divided into a plurality of sections 22, the plurality of sections 22 being defined by upper and lower tube sheets 23, 24 and channels 25 between the plurality of sections 22, wherein the width of the channels is the heat exchange tube bundle 20.25-2.0 times the diameter of the tube); and selecting the number of multiple segments 22 in the heat exchange tube bundle (for a heat exchange tube bundle having a circular cross-section) according to the mathematical relationship described above.
The valve 19 for supplying the liquid feed and the water condensate of the dehydrogenation process to the shell side of the proposed heat exchanger may be equipped with nozzles for injection and fine atomization of these streams.
The heat exchange tube bundle 2 in the proposed heat exchanger 11 may have a circular, rectangular, trapezoidal, etc. shape in horizontal cross-section.
The plurality of segments 22 may have a triangular, square, trapezoidal, polygonal, etc. shape in horizontal cross-section.
To facilitate clean removal of deposits of hot polymer from the outer surfaces of the heat exchanger tubes during repair and restoration work, the heat exchanger tube bundle 2 may have an in-line (square-marked) arrangement, as well as a removable tube sheet.
The shell 1 of the heat exchanger 11 may be equipped with auxiliary valves for monitoring the process by measuring temperature and pressure along the height and cross section of the shell 1.
Drawings
Fig. 1 shows a diagram of a proposed heat exchanger 11 for utilizing the exit C3-C5The contact gas of the paraffinic dehydrogenation reactor superheated the feed steam in countercurrent. The heat exchanger 11 includes: shell (shell) 1, heat exchange tube bundle (tube side)2, lower tube sheet 3 and upper tube sheet 4, tubes 5 and distribution chamber 6 for introducing contact gas into heat exchange tubes 2 of heat exchanger 11, collection chamber 7 and tubes 8 for discharging cooled contact gas from heat exchanger 11, tubes 9 for introduction and tubes 10 for discharging superheated feed vapor from the shell side of heat exchanger 11, valves 12 for introducing a portion of the feed in liquid form into the shell side of heat exchanger 11, segmented transverse baffles 13, additional spaced baffles 14, fins 15 bent downward at 30 °. The heat exchanger 11 may have a floating head (collection chamber 7) with a bellows 16, which bellows 16 is located in the lower part of the housing 1. Fig. 2, 3, 4 and 6 show cross-sections of some variants of the heat exchange tube bundle 2.
Fig. 2 shows an embodiment of the invention with valve 12 for supplying the feed in liquid form without separating heat exchange tube bundle 2 into sections 17.
Fig. 3 shows an embodiment of a heat exchanger tube bundle 2 divided into sections 17 by channels 18 and having valves 12 (not shown) for supplying a portion of the feed in liquid form.
Fig. 4 shows an embodiment of a heat exchange tube bundle 2, which heat exchange tube bundle 2 is divided into a plurality of sections 17 by channels 18 and has valves 12 arranged opposite to open inlets for introducing feed vapor into the channels 18 and outlets for discharging feed vapor from the channels 18, which outlets are closed by the walls of the shell 1.
The proposed solution of a shell-and-tube heat exchanger for cooling C between stages of turbochargers in a contact gas condenser unit at high pressure with counter-flow of cooling process water is shown in fig. 5 and 64A contact gas for dehydrogenation of hydrocarbons. A valve 19 for supplying process water condensate to the shell side of the heat exchanger is located on a line 20 supplying contact gas to the heat exchanger and in the upper part of the shell at the level of the location of tubes 21 for introducing contact gas into the heat exchanger and/or a heat exchange tube bundle which is divided into a plurality of sections 22, the plurality of sections 22 being defined by upper and lower tube sheets 23, 24 and channels 25 between the plurality of sections 22. The heat exchanger is further provided with a conduit 26 for outputting cooled contact gas, an input 27 and an output 28 for cooling water.
Detailed Description
The proposed heat exchanger for heating the feed vapor is in the example of a plant for the preparation of isobutene (subsequently using the isobutene obtained in the synthesis of methyl tert-butyl ether (MTBE)) by dehydrogenation of isobutane in a fluidized bed of a chromia-alumina catalyst, taking into account the operation of this heat exchanger. The design of the heat exchanger used is shown in fig. 1-4.
In a fluidised bedIn the reactor, at 165hr-1At an isobutene feed space velocity (space velocity) of 20% Cr2O3、2％K2O、2％SiO2And 76% Al2O3Is dehydrogenated over a fine-grained catalyst. The composition of the feed is given in table 1. The feed stream in liquid form at a pressure of 885kPa entered an evaporation station in an amount of 28.123t/h where it was sequentially evaporated, then heated by a supplied vapor and delivered in vapor form at a temperature of 70 ℃ to be further heated in the proposed shell-and-tube heat exchanger placed on the line for the contact gas leaving the reactor. The heat exchanger shell has a diameter of 1.4m, the number of tubes is 1306, and the tubes have a diameter of 25.4 mm. The length of the heat exchanger tubes was 10.6 m. Feed vapor enters the shell side of heat exchanger 11 through line 9. A portion of the feed in liquid form was injected through a nozzle into the middle of the shell side at a temperature of 19.3 ℃. The following is the result of the operation of the apparatus in various modes and heat exchanger designs. The run time of the device in each mode was 4000 hours.
In example 1, a heat exchanger 11 having a heat exchange tube bundle 2 shown in fig. 2 (closest prior art) was used. In the case where no part of the feed in liquid form is supplied (operating conditions of the prior art), at the end of the plant operation, an increase in pressure from 423kPa at the start of operation to 567kPa at the end of operation (close to the maximum pressure allowed under conditions complying with the heat exchanger strength) is observed in the shell 1 of the heat exchanger 11 (at the input of the feed vapour to the heat exchanger), which requires a reduction in the feed load of the reactor to 25.7 t/h. At the same time, the pressure at the compressor inlet and correspondingly in the upper part of the reactor increased from 137kPa to 165kPa due to the temperature increase of the contact gas at the compressor inlet. All this leads to a reduction in the dehydrogenation performance (reduction in the productivity of the plant and in the isobutene yield, calculated on the decomposed isobutane, from 88.2% to 85.1% by weight). When the heat exchanger was opened after shutdown, significant polymer deposits were found in the upper high temperature portion of the shell side of the heat exchanger.
In example 2, a heat exchanger 11 with a heat exchange tube bundle 2 shown in fig. 2 was used, wherein a valve 12 for injecting the liquid feed was arranged at a distance of 50% of the height of the shell 1 from the upper tube sheet 4. The steady state mode of the plant remained stable throughout the run time when a portion of the liquid feed was supplied to the shell side of the heat exchanger in an amount of 45% of the total feed of feed for dehydrogenation (see table 2). During operation of the apparatus, no pressure increase in the shell of the heat exchanger was observed. The reactor feed load was kept constant.
The yield of olefins did not decrease during the run and the isobutene yield reached 41.2 wt% based on isobutane passed and 88.0 wt% based on isobutane decomposed. The steam consumption directed to the feed evaporator and to the resulting feed steam heater is reduced. The performance of the dehydrogenation unit remains stable. When the heat exchanger was open, no hot polymer deposits were observed in the shell side. In the upper high-temperature zone of the heat exchanger, the temperatures of the feed vapors at the heat exchanger outlet were respectively 410 ℃. As the feed of the feed portion in liquid form increased to 45% and the feed fraction in vapor form decreased accordingly, the vapor (single run average) used to vaporize and heat the feed in example 2 saved 2.56t/h compared to the closest prior art (6.29 t/h).
In example 3, a heat exchanger 11 having the heat exchange tube bundle 2 shown in fig. 2 was used. When a portion of the liquid feed was supplied to the shell side of the heat exchanger in an amount of 15% of the total feed for dehydrogenation, the pressure in the heat exchanger shell (at the input of feed vapor into the heat exchanger) was observed to increase to 510kPa at the end of the run. At the same time, the pressure at the compressor inlet and correspondingly in the upper part of the reactor increased to 152kPa as a result of the temperature increase of the contact gas at the compressor inlet. This resulted in a reduction in the yield of isobutene to 86.3 wt% based on the decomposed isobutane. When the heat exchanger was opened after shutdown, significant polymer deposits were found in the upper high temperature portion of the shell side of the heat exchanger.
In example 4, a heat exchanger 11 having a heat exchange tube bundle 2 shown in fig. 3 was used, the heat exchange tube bundle 2 having channels 18 having a width equal to 2.0 times the diameter of the heat exchange tubes. The shell 1 of the heat exchanger 11 comprises a valve 12 for introducing the liquid feed into the shell side. A valve 12 for feeding a portion of the feed in liquid form to the shell side is disposed opposite to the passage 18 between the plurality of sections 17 in the flow direction of the feed vapor. When a portion of the liquid feed was supplied to the shell side of the heat exchanger in an amount of 15% of the total supply of feed for dehydrogenation, no plugging of the shell side by the hot polymer was observed. The performance of the equipment remains stable during operation: the isobutene yield based on the isobutane passed was 40.9 wt% and the isobutene yield based on the isobutane decomposed was 88.5 wt%. The steam savings is 0.68t/h compared to the closest prior art.
In example 5, a heat exchanger 11 having a heat exchange tube bundle 2 shown in fig. 4 was used, the heat exchange tube bundle 2 having channels 18 having a width equal to 0.25 times the diameter of the heat exchange tubes. No liquid feed supply to the heat exchanger 11 was performed. No blocking of the shell side by hot polymer was observed. The performance of the equipment remains stable during operation: the isobutene yield based on the isobutane passed was 41.1 wt% and based on the isobutane decomposed was 88.3 wt%.
When a portion of the liquid feed was supplied to valve 12 in an amount of 30% of the total supply of feed, the run time without plugging increased to 8000 hours.
The operation of the heat exchanger proposed for cooling under pressure the C between the turbochargers of a contact gas condenser unit in an embodiment of a plant for the production of butadiene by the oxidative dehydrogenation of n-butenes is taken into account4A contact gas for dehydrogenation of hydrocarbons. The design of the heat exchanger used is shown in fig. 5 and 6.
A process for the oxidative dehydrogenation of n-butenes to butadiene in the presence of steam and oxygen (in the form of a mixture of oxygen and air) in an adiabatic reactor with a fixed bed of iron magnesium zinc phosphate-containing catalyst. Dehydrogenation stripThe following parts: c4H8：O2：H2The molar ratio of O is 1: 0.58: 17; the space velocity of n-butene feeding is 300 hours-1. The temperature at the inlet of the catalyst bed was 250 ℃ and the outlet bed temperature was 580 ℃. The pressure below the catalyst bed at the start of the test was 175 kPa. Feed streams to the reactor (in t/h): n-butene: 15.0, oxygen: 4.97, nitrogen: 19.83, steam: 81.6. the contact gas in the process was sent at a temperature of 580 ℃ in an amount of 112.4t/h to a waste heat boiler where its temperature was reduced to 220 ℃ and a secondary vapour was obtained, which was then sent to a quench two-stage scrubber where it was cooled to 110 ℃ by direct contact with circulating water. After quenching, the contact gas is sent to a contact gas compressor unit. The composition of the feed, the composition after the dehydrogenation reactor and the steam cooling and condensing unit, and the composition of the process water condensate are shown in table 2.
Compression of contact gas in
(Prague, Czechoslovakia) in a three-stage five-wheel turbocharger "Viola-TP". The turbocharger has two interstage surface coolers. The main features of the apparatus contacting the gas compressor unit are as follows:
turbocharger productivity (m)3Hour): 15400
Discharge pressure (kPa): 1300
Rotor speed (rpm): 9900
Number of wheels in rotor (pcs): 5,
the first stage intercooler (vertical shell and tube heat exchanger) is designed to cool the contact gas entering the suction inlet of the second compression stage:
heat transfer surface (m)2)：200
Diameter (mm) of case (housing): 1500
Number of tubes (25X 2X 2000 mm): 1400 are provided with
The second stage intercooler (vertical shell and tube heat exchanger) is designed to cool the contact gas entering the suction inlet of the third compression stage:
heat transfer surface (m)2)：140
Diameter (mm) of case (housing): 1300
Number of tubes (25X 2X 2000 mm): 1200 are provided with
The liquid separator after the first compression stage is designed to separate and remove process water condensate:
volume (m)3)：1,675
Diameter (mm) of case (housing): 1085
Length (mm) of the cylindrical portion of the housing: 1500,
the liquid separator after the second compression stage is designed to separate and remove process water condensate:
volume (m)3)：0.76
Diameter (mm) of case (housing): 800
Length (mm) of the cylindrical portion of the housing: 1100.
the contact gas, at a temperature of 24 ℃ and a pressure of 120kPa, was led from the suction header (first rotor blade wheel) to the first compression stage (first compressor wheel) via a line of 450mm diameter which was connected to the turbocharger inlet, and the contact gas, at a temperature of 68 ℃ and a pressure of 150kPa, was fed via a line of 400mm diameter to the shell side of the interstage cooler of the first stage for cooling, where it was cooled to 36 ℃ by industrial water circulating through the tube side in countercurrent to the contact gas. The contact gas is then sent to a separator to remove process water condensate and fed to the suction of the second compression stage of the turbocharger via a line having a diameter of 400 mm. After passing through the second compression stage (second rotor wheel and third rotor wheel), the contact gas, having a temperature of 82 ℃ and a pressure of 480kPa, was conveyed through a 200mm line to the interstage cooler of the second stage, where it was cooled to 32 ℃. The contact gas was then passed through a separator to remove process water condensate before it was fed to the suction of the third compression stage via a line of 200mm diameter. After passing through the third stage at a temperature of 71 ℃ and a pressure of 1120kPa, the gas enters a discharge header from which the gas is led to the recovery of butadiene.
Example 6 (closest prior art): the vapour condensate obtained by condensing the vapour is introduced into the contact gas stream immediately after each compression stage and correspondingly before and at a distance of 500mm from the intercoolers (see table 5). The condensate was fed at a temperature of 40 ℃ and a pressure of 600kPa in an amount of 0.1 kg condensate per kg contact gas. At the end of the test, after 1200 hours from the start of operation, the turbocharger stopped receiving the load and the motor current decreased from 190A at the start of the test to 130A at the end of the test. In this case, the pressure suddenly increases in the compression stage of the turbocharger and, correspondingly, the pressure below the catalyst bed in the dehydrogenation reactor. Polymer-induced clogging was observed in the impeller and guide vanes of the turbocharger and the shell side of the interstage heat exchanger when the compressor was on. The butadiene yield based on the passed n-butenes was 49.9 wt% and the butadiene yield based on the decomposed n-butenes was 81.5 wt%.
Example 7: the process conditions were the same as in example 6.
The difference from example 6 is that a heat exchanger with a valve arranged on the line supplying the contact gas to the heat exchanger is used, and in the upper part of the shell and at the level of the position of the contact gas inlet conduit of the heat exchanger, the valve is used for supplying the process condensate to the shell side (see fig. 5). At the same time, process water condensate was injected into the contact gas in an amount of 0.1 kg of process water condensate per kg of contact gas at a temperature of 40 ℃ and a pressure of 6 atm. At the end of the test, after 2000 hours, no deviation of the turbocharger operating mode was observed. When the compressor and interstage heat exchanger were turned on, no polymer deposits were observed. The dehydrogenation performance achieved was as follows: the butadiene yield based on the passed n-butenes was 51.3 wt% and the butadiene yield based on the decomposed n-butenes was 83.5 wt%.
Example 8: the process conditions were the same as in example 6. The difference from example 6 is that a heat exchanger having a heat exchange tube bundle divided into a plurality of sections 22 is used, the plurality of sections 22 being defined by upper and lower tube sheets 23 and 24 and channels 25 between the plurality of sections 22, the width of the channels being 1.0 times the diameter of the heat exchange tubes. Figure 6 represents a schematic view of a heat exchange tube bundle. The process condensate is not supplied to the heat exchanger. At the end of the test, a slight pressure increase was observed upstream of the compressor and below the catalyst bed in the dehydrogenation reactor after 1500 hours from the start of the run. At the same time, the current drawn by the compressor motor is slightly reduced, which indicates that the load on the compressor is slightly reduced (i.e., the compressor begins to receive a slightly smaller amount of gas). When the compressor and interstage heat exchangers were turned on at the end of the run, insignificant polymer deposits were observed on the blades of the stage I and II impellers and in the flow parts (flow part) of the compressor. The interstage heat exchanger surface is clean. The dehydrogenation performance achieved was as follows: the butadiene yield from passed n-butenes was 51.1 wt%, and the butadiene yield from decomposed n-butenes was 82.3 wt%.
Thus, the technical effect of the claimed invention is to increase C over the closest prior art3-C5The productivity of the hydrocarbon dehydrogenation plant and reduces operating costs.
Industrial applicability
For in C3-C5The shell-and-tube heat exchanger for heating the feed vapor in the dehydrogenation of paraffinic hydrocarbons can be used for the production of the main monomers for synthetic rubbers, and for the production of polypropylene, methyl t-butyl ether, etc.
TABLE 1
| Components | Composition of feed in wt% |
| Propane | 0.9 |
| Propylene (PA) | 0.03 |
| Isobutane | 97.8 |
| Isobutene | 0.09 |
| N-butane | 0.75 |
| 1-butene | 0.13 |
| Trans-2-butene | 0.07 |
| Cis-2-butene | 0.14 |
| Butadiene | 0.01 |
| C5 and above | 0.002 |
| Water (W) | 0.008 |
| Dimethyl ether | 0.0068 |
| Methanol | 0.071 |
| Tert-butyl alcohol | 0.0003 |
| Methyl tert-butyl ether MTBE | 0.0003 |
| Total of | 100 |
TABLE 2
Claims (22)
1. A shell-and-tube counterflow heat exchanger for use in the process of3-C5A process for the dehydrogenation of paraffinic hydrocarbons wherein the heat of the contact gas leaving the dehydrogenation reactor is used to heat the feed vapor, said heat exchanger comprising: a vertical cylindrical housing (1); a heat exchange tube bundle (2) having an upper tube sheet (4) and a lower tube sheet (3); a conduit (5) and a distribution chamber (6) for introducing a contact gas into the upper part of the tube side (2) of the heat exchanger (11); a collection chamber (7) and a conduit (8) for discharging cooled contact gas from a lower portion of the tube side; a conduit (9) for introducing feed vapor into the shell side of the heat exchanger (11), wherein the shell side is divided into a plurality of sections by segmented horizontal transverse baffles (13); and a conduit (10) for withdrawing heated feed vapor from the shell side, characterized in that the heat exchanger (11) comprises a valve (12), the valve (12) being adapted to supply a portion of the feed supplied in liquid form to the heat exchanger (11) to the shell side of the heat exchange tube bundle (2) and/or to the shell side of the heat exchange tube bundle (2) divided into a plurality of sections (17), the plurality of sections (17) being formed by the upper tube sheet (4) and the lower tube sheet (3) to remove heated feed vapor from the shell side, the heat exchanger (11) comprising a valve (12) for supplying a portion of the feed supplied in liquid form to the shell side of the heat exchangeAnd vertical channels (18) between said plurality of segments (17).
2. A shell and tube heat exchanger according to claim 1, characterized in that the width of the channels (18) between the sections (17) is 0.25-2.0 times the diameter of the heat exchange tubes.
3. A shell and tube heat exchanger according to any one of claims 1 and 2, characterized in that the valve (12) for supplying a portion of the feed in liquid form into the shell side is arranged in the upper part of the shell (1) at a distance from the upper tube sheet (4) of the heat exchanger (11), wherein the distance is 15-50% of the height of the shell (1).
4. A shell and tube heat exchanger according to any one of claims 1 to 3, characterized in that the heat exchange tube bundle (2) in each section has 1-3 further horizontal transverse baffles (14) spacing the heat exchange tubes, wherein 1-4 spaced transverse baffles (14) are located in the upper part of the heat exchange tube bundle (2) below the upper tube sheet (4), having fins (15), which fins (15) abut the edges of the further spaced transverse baffles (14) at the outlet of the feed vapor from the heat exchange tube bundle (2), which fins are bent downwards in the flow direction of the feed vapor at an angle of 20 ° to 40 °.
5. A shell and tube heat exchanger according to any one of claims 1 to 4, characterized in that the valve (12) for supplying a portion of the feed in liquid form into the shell side is arranged opposite to the channel (18) between the sections (17) in the flow direction of the feed vapor.
6. A shell and tube heat exchanger according to any one of claims 1 to 5, characterized in that the channels (18) between the sections (17) have an open inlet for feed vapor and an outlet closed by the wall of the shell (1).
7. A shell and tube heat exchanger according to any one of claims 1 to 6, characterized in that the heat exchange tube bundle (2) has a circular, rectangular or trapezoidal shape in horizontal cross-section.
8. A shell and tube heat exchanger according to any one of claims 1 to 7, characterized in that the plurality of segments (17) in the heat exchange tube bundle (2) has a triangular, square, rectangular or trapezoidal shape in horizontal cross-section.
9. A shell and tube heat exchanger according to any one of claims 1 to 8, characterized in that the heat exchange tube bundle (2) has an in-line (square-marked) tube arrangement.
10. A shell and tube heat exchanger according to any one of claims 1 to 9, characterized in that the tube sheet is detachable.
11. A shell and tube heat exchanger according to any one of claims 1 to 10, characterized in that the valve (12) for supplying liquid feed is equipped with nozzles for injection and atomization of feed.
12. A shell and tube heat exchanger for cooling C under pressure between turbocharger stages of a contact gas condenser unit using counterflow of cooling process water4A contact gas for a hydrocarbon dehydrogenation process, said heat exchanger comprising: a vertical cylindrical housing; a heat exchange tube bundle having an upper tube sheet (23) and a lower tube sheet (24); a conduit (27) and distribution chamber for introducing cooling water into the lower portion of the tube side of the heat exchanger; a collection chamber and conduit (28) for discharging hot water from an upper portion of the tube side; a conduit (21) for introducing a contact gas into the shell side of the heat exchanger, wherein the shell side is divided into a plurality of sections by segmented horizontal transverse baffles; and a conduit (26) for discharging cooled contact gas from the shell side, the heat exchanger being characterized byIt comprises a valve (19), said valve (19) being arranged on the line (20) supplying the contact gas to the heat exchanger and/or in the upper part of the heat exchanger shell for supplying the water condensate of the dehydrogenation process to the shell side of the heat exchanger tube bundle and/or to the shell side of the heat exchanger tube bundle divided into a plurality of sections (22), said plurality of sections (22) being defined by an upper tube sheet (23) and a lower tube sheet (24) and vertical channels (25) between said plurality of sections (22).
13. A shell and tube heat exchanger according to claim 12, characterized in that it comprises said valve (19) at the level of said conduit (21), said conduit (21) being used for introducing contact gas into the heat exchanger.
14. A shell and tube heat exchanger according to any one of claims 12 and 13, characterized in that the width of the channels (25) between the sections (22) is 0.25-2.0 times the heat exchange tube diameter.
15. A shell and tube heat exchanger according to any one of claims 12 to 14, characterized in that the valve (19) is arranged opposite to the channel (25) between the sections (22) in the flow direction of the contact gas.
16. A shell and tube heat exchanger according to any one of claims 12 to 15, characterized in that the channels (25) between the sections (22) have an open inlet for contacting gas and an outlet closed by the wall of the shell.
17. A shell and tube heat exchanger according to any one of claims 12 to 16, characterized in that the heat exchange tube bundle has a circular, square, rectangular or trapezoidal shape in horizontal cross-section.
18. A shell and tube heat exchanger according to any one of claims 12 to 17, characterized in that the plurality of segments (22) in the heat exchange tube bundle have a triangular, square, rectangular or trapezoidal shape in horizontal cross-section.
19. A shell and tube heat exchanger according to any one of claims 12 to 18, characterized in that the heat exchange tube bundle has an in-line (square-numbered) tube arrangement.
20. A shell and tube heat exchanger according to any one of claims 12 to 19, wherein the tube sheet is removable.
21. A shell and tube heat exchanger according to any one of claims 12 to 20, characterized in that the valve (19) is equipped with nozzles for injection and atomization of water condensate for the dehydrogenation process.
22. A shell and tube heat exchanger according to any one of claims 12 to 21, characterized in that the heat exchange tube bundle has a circular shape in horizontal cross-section, the number of said plurality of segments (22) in the heat exchange tube bundle being selected according to the following relation:
Nsegment of＝KP/9h，
Wherein N isSegment ofIs the number of the plurality of segments in the tube bundle;
k is a rounding factor, varying between 1.0 and 1.5;
h is the tube bundle spacing;
p is the circumference of the outer tubes in the tube bundle.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2017130788A RU2642440C1 (en) | 2017-08-30 | 2017-08-30 | Shell-and-tube heat exchangers in processes of hydrocarbon degradation c3-c5 (versions) |
| RU2017130788 | 2017-08-30 | ||
| PCT/RU2018/000562 WO2019045599A1 (en) | 2017-08-30 | 2018-08-27 | Shell-and-tube heat exchangers in processes for the dehydrogenation of с3-с5 hydrocarbons (variants) |
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| Publication Number | Publication Date |
|---|---|
| CN110770520A true CN110770520A (en) | 2020-02-07 |
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|---|---|---|---|
| CN201880038577.8A Pending CN110770520A (en) | 2017-08-30 | 2018-08-27 | For C3-C5Shell-and-tube heat exchanger in a process for dehydrogenation of hydrocarbons (variants) |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN110770520A (en) |
| RU (1) | RU2642440C1 (en) |
| WO (1) | WO2019045599A1 (en) |
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| CN114459263B (en) * | 2020-10-21 | 2023-08-29 | 中国石油化工股份有限公司 | Heat exchanger, butene oxidative dehydrogenation device and method for preparing butadiene by butene oxidative dehydrogenation |
| RU2767682C1 (en) * | 2020-11-30 | 2022-03-18 | Общество с ограниченной ответственностью Торговый дом "Кемеровский экспериментальный завод средств безопасности" | Gas heat-and-power complex, heat exchanger of gas heat-and-power complex and method of hot air supply for plenum ventilation of rooms, implemented with their help |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010125037A1 (en) * | 2009-04-29 | 2010-11-04 | Basf Se | Shell and tube heat exchanger and method for removing volatile substances from a polymer solution |
| RU135099U1 (en) * | 2013-05-20 | 2013-11-27 | Общество с ограниченной ответственностью "ТюменНИИгипрогаз" | SHELL-TUBULATED HEAT EXCHANGER |
-
2017
- 2017-08-30 RU RU2017130788A patent/RU2642440C1/en active
-
2018
- 2018-08-27 CN CN201880038577.8A patent/CN110770520A/en active Pending
- 2018-08-27 WO PCT/RU2018/000562 patent/WO2019045599A1/en active Application Filing
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| SU1132139A1 (en) * | 1982-09-20 | 1984-12-30 | Предприятие П/Я А-1345 | Shell-and-tube heat exchanger |
| JPS6438591A (en) * | 1987-08-04 | 1989-02-08 | Toshiba Corp | Heat exchanger |
| CN1117575A (en) * | 1995-04-17 | 1996-02-28 | 哈尔滨工程大学 | Glass tube low temp. heat exchanger |
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| RU147654U1 (en) * | 2014-07-18 | 2014-11-10 | Общество с ограниченной ответственностью "ТюменНИИгипрогаз" | SHELL-TUBULATED HEAT EXCHANGER |
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| WO2019045599A1 (en) | 2019-03-07 |
| RU2642440C1 (en) | 2018-01-25 |
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