CN112705114A - Heat exchange type multiphase reactor, application method thereof and light gasoline etherification method - Google Patents

Heat exchange type multiphase reactor, application method thereof and light gasoline etherification method Download PDF

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CN112705114A
CN112705114A CN201911015979.9A CN201911015979A CN112705114A CN 112705114 A CN112705114 A CN 112705114A CN 201911015979 A CN201911015979 A CN 201911015979A CN 112705114 A CN112705114 A CN 112705114A
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reaction
heat exchange
heat
zone
etherification
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CN112705114B (en
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袁清
王少兵
毛俊义
黄涛
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or 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
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/20—Organic compounds not containing metal atoms
    • C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

A heat exchange type multiphase reactor comprises a reactor shell, a top feed inlet, a middle feed inlet, fluid collecting, mixing and distributing equipment, a top outlet, a reaction product outlet and an optional external condenser, wherein the reactor shell comprises an upper heat exchange area and a lower reaction area, the heat exchange area is filled with filler or provided with a tower plate, at least two catalyst bed layers are arranged in the reaction area, the middle feed inlet and the fluid collecting, mixing and distributing equipment are arranged on each catalyst bed layer, and the bottom of the reaction area is provided with a reaction product outlet. The device is mainly suitable for a solid-phase catalytic exothermic equilibrium reaction or a strong exothermic reaction system of liquid-phase or gas-liquid feeding, and effectively takes away reaction heat release in a mode of material self vaporization and feeding direct contact heat exchange and material cooling backflow so as to achieve the purpose of improving equilibrium conversion rate or controlling reaction temperature.

Description

Heat exchange type multiphase reactor, application method thereof and light gasoline etherification method
Technical Field
The invention relates to reactor equipment in the field of petrochemical industry and an application method thereof, in particular to a fixed bed reactor for a gas-liquid mixed phase reaction system of exothermic reaction and an application method thereof.
Technical Field
The fixed bed reactor is a reactor form filled with solid catalyst or solid reactant to realize heterogeneous reaction process, and has the advantages of simple structure, convenient operation, stable operation, small fluid back mixing, small mechanical loss of catalyst, etc. and is the most widely used reactor form in industry at present. The structure types of the fixed bed reactor are mainly divided into an adiabatic type and a heat exchange type, wherein the adiabatic type fixed bed is suitable for exothermic reaction with small reaction heat effect, the reaction process allows the reaction with wider variation range of temperature, the heat effect is larger, but the process is not very sensitive to the reaction temperature or the reaction rate is very fast; the heat exchange type fixed bed refers to a reaction device which takes away reaction heat by adopting a heat exchange medium.
In order to ensure the filling of the catalyst and the better distribution and flow of the fluid in the fixed bed reactor, a certain internal member needs to be installed inside the reactor, the commonly used internal members of the reactor mainly comprise various distributors, collectors, supporting structures and the like, CN201020000158.6 discloses a liquid collecting, mixing and distributing device, which is characterized in that a plurality of labyrinth members for enhancing the mixing of the fluid are arranged inside the device, and CN100430458C discloses a mixing device with vertically arranged vortex chambers, which mainly aims at mixing the fluid and uniformly distributing the mixed fluid on the next bed layer.
Etherification, which is generally the reaction of methanol with tertiary olefins such as isobutylene and isoamylene to produce tertiary methyl alkyl ether (MTBE, TAME, etc.), is a typical exothermic reaction process controlled by thermodynamic equilibrium. The currently used forms of etherification reactors in industry mainly comprise fixed beds, expanded beds and catalytic distillation columns. The expanded bed etherification reactor (FR 2455019, FR 2440931) firstly proposed by IFP can effectively eliminate reaction hot spots, but the material backmixing is serious, so that the conversion rate is reduced; the catalytic distillation technology (US4439350, CN 1022382) is used for etherification reaction, which is beneficial to breaking equilibrium limitation and improving reaction conversion rate, but the catalyst filling structure in the catalytic distillation tower is relatively complex.
In order to solve the heat release problem in the chemical reaction process, a tubular reactor or a cylindrical reactor with reaction materials cooled in an external circulation mode is adopted in the traditional process. The tubular reactor has the advantages of complex equipment, large investment, high energy consumption and less application; and the reaction efficiency of the external circulation drum type reactor is reduced because the concentration of reactants is diluted by the circulating material flow. Patent CN 200977456a discloses a bubble point reactor for preparing MTBE, wherein the reaction is carried out in the range of the bubble point and dew point temperature of the materials, and part of the liquid component absorbs the reaction heat to form a vapor phase, and then flows out from a vapor phase pipeline arranged at the top of the reactor, thereby achieving the effect of controlling the reaction temperature. However, this reactor is not suitable for feedstocks with too high an olefin content, since the heat of reaction vaporizes all of the methanol-C4 azeotrope and even the remaining C4, and the remaining heat also causes the bed temperature to continue to rise, leading to reverse decomposition of MTBE.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a fixed bed reactor of a solid catalytic reaction system, wherein the reaction feeding is liquid phase or gas-liquid two-phase, and the fixed bed reactor is used for the reaction process of strong heat release or thermodynamic equilibrium control, and an application method thereof.
The second technical problem to be solved by the invention is to provide a light gasoline etherification reaction method.
The invention provides a heat exchange type multiphase reactor, which consists of a reactor shell, a top feed inlet, a middle feed inlet, fluid collecting, mixing and distributing equipment, a top outlet and a reaction product outlet, wherein the reactor shell comprises an upper heat exchange zone and a lower reaction zone, the top feed inlet and the top outlet are arranged at the top of the heat exchange zone, the heat exchange zone is filled with filler or provided with a column plate, at least two catalyst bed layers are arranged in the reaction zone, the middle feed inlet and the fluid collecting, mixing and distributing equipment are arranged above the catalyst bed layers, and the bottom of the reaction zone is provided with the reaction product outlet.
The application method of the heat exchange type multiphase reactor adopts the heat exchange type multiphase reactor, the reaction zone is filled with at least two sections of catalyst bed layers, one part of reaction raw materials are introduced into the heat exchange zone from a top feed inlet, directly contact with reaction raw material steam from the reaction zone for heat exchange, then enter the reaction zone and contact with the catalyst for exothermic reaction, the other part of reaction raw materials are introduced from a middle feed inlet, are fully mixed and heat exchanged with reaction material flow from an upper layer through fluid collecting, mixing and distributing equipment, are uniformly distributed and enter the next section of catalyst bed layer for continuous reaction, and reaction products after the reaction are discharged out of the reactor from a reaction product outlet at the bottom of the reaction zone.
A method for etherifying light gasoline includes such steps as filling at least two solid acid catalyst beds in reaction region, introducing the mixture of light gasoline and methanol to heat exchange region from top inlet, directly contacting with the vaporized steam from reaction region for heat exchange, contacting with catalyst, etherifying reaction of active olefin and methanol in light gasoline, introducing the other part of mixture of etherifying raw material to intermediate inlet, mixing with the reaction material from upper layer, heat exchanging, uniformly distributing, and discharging the gasoline from reactor.
The heat exchange type multiphase reactor and the application method thereof provided by the invention have the beneficial effects that:
(1) the reaction temperature is controlled in a narrow range by utilizing the self vaporization heat absorption of the reaction materials and the reflux heat exchange of the cooling materials, so that the reaction selectivity and the conversion rate are improved.
(2) The upper section of the reactor is provided with the heat exchange area, so that the direct contact heat exchange of the vaporized materials and the fresh feeding materials is realized, the preheating of the raw materials and the condensation of the vaporized materials are realized, and the high-efficiency utilization of reaction heat is realized.
(3) The fluid collecting, mixing and distributing system can efficiently and quickly distribute and collect reaction fluid, and effectively solves the problems of uneven distribution of fluid in a bed layer in a multi-section heat-insulating fixed bed reactor and longer mixing degree of fluid among sections in the prior art.
Drawings
FIG. 1 is a schematic diagram of a heat exchange multiphase reactor;
fig. 2 is a schematic structural diagram of a fluid collecting, mixing and distributing device.
FIG. 3 is a three-dimensional schematic view of a spiral baffle within the secondary mixing chamber.
Wherein:
1-a top feeding hole, 2-a reaction zone, 3-a heat exchange zone, 4-a fluid collecting, mixing and distributing device, 5-a catalyst bed layer, 6-a gas phase outlet, 7-a pressure control valve, 8-a condenser, 9-a heat exchange zone reflux port, 10-a middle feeding hole and 11-a reaction product outlet; 12-guide plate, 13-external feeding distribution pipe, 14-primary mixing chamber, 15-secondary mixing chamber, 16-distribution plate and 17-bottom support plate.
Detailed Description
In the following, a detailed description of the present invention is given, wherein the top of the container is defined as the position from 0-5% of the container from top to bottom, the upper portion is defined as the position from 0-50% of the container from top to bottom, the lower portion is defined as the position from 50-100% of the container from top to bottom, and the bottom is defined as the position from 95-100% of the container from top to bottom.
The invention provides a heat exchange type multiphase reactor, which consists of a reactor shell, a top feed inlet, a middle feed inlet, fluid collecting, mixing and distributing equipment, a top outlet and a reaction product outlet, wherein the reactor shell comprises an upper heat exchange zone and a lower reaction zone, the top feed inlet and the top outlet are arranged at the top of the heat exchange zone, the heat exchange zone is filled with filler or provided with a column plate, at least two catalyst bed layers are arranged in the reaction zone, the middle feed inlet and the fluid collecting, mixing and distributing equipment are arranged above the catalyst bed layers, and the bottom of the reaction zone is provided with the reaction product outlet.
When the heat exchange area adopts the filler to provide the heat exchange surface, preferably, the top of the heat exchange area is provided with an inlet distribution device, and the inlet distribution device adopts a conventional liquid phase distributor, such as a branch pipe type, a ring pipe type, a trough disc type or a spray type distribution device. When the heat exchange area adopts the tower plate to provide the heat exchange surface, a downcomer can be used for feeding.
Preferably, the fluid collecting, mixing and distributing device comprises a top support plate, a guide plate, an external fluid distribution pipe, a mixing chamber, a fluid distribution disc and a bottom support plate which are spaced from top to bottom, wherein the mixing chamber consists of an external annular primary mixing chamber and a central secondary mixing chamber; the external fluid distribution pipe is a circular or grid pipeline with small holes and is communicated with the middle feed inlet; the fluid distribution plate is provided with small holes.
Preferably, the guide plate is a conical plate, and the cone angle is 140-175 degrees.
Preferably, the secondary mixing chamber is surrounded by an inner layer and an outer layer of cylindrical barrels with openings, a guide plate at the top and a bottom plate with a circular opening. The inner layer cylindrical barrel is the inner barrel of the secondary mixing chamber, and the outer layer cylindrical barrel is the outer barrel of the secondary mixing chamber.
Preferably, the diameter of the cylinder in the secondary mixing chamber is 1/3-3/4 of the diameter of the outer cylinder.
Preferably, the openings of the inner and outer cylinders of the secondary mixing chamber are arranged in a staggered order on the circumference, the diameter of the opening of the outer cylinder is 5-50mm, preferably 6-30mm, and the diameter of the opening of the inner cylinder is 3-40mm, preferably 5-25 mm.
Preferably, the external fluid distribution pipe is a circular ring pipe, the pipe diameter of the ring pipe is 20-200mm, more preferably 30-150mm, round holes with the diameter of 2-20mm are formed in the ring pipe, and the distance between the round holes is 10-200mm, preferably 20-100 mm.
Preferably, staggered baffles are distributed in the secondary mixing chamber, and the baffles can be rectangular, spiral, folded rectangular and the like, or wire mesh and corrugated packing to enhance mixing strength.
The diameters of the heat exchange zone and the reaction zone can be designed to be the same or different according to the vaporization quantity. Preferably, the ratio of the diameter of the heat exchange zone to the diameter of the reaction zone is (0.5-1.0): 1, and the height ratio is (0.1-0.5): 1.
Preferably, the top outlet is communicated with the upper part of the heat exchange zone and/or the middle feed inlet of the reaction zone through a condensation cooler.
An application method of a heat exchange type multiphase reactor adopts any one of the heat exchange type multiphase reactors, the reaction zone is filled with at least two sections of catalyst bed layers, one part of reaction raw materials are introduced into the heat exchange zone from a top feed inlet, directly contact with reaction raw material steam from the reaction zone for heat exchange, then enter the reaction zone and contact with a catalyst for exothermic reaction, the other part of reaction raw materials are introduced from a middle feed inlet, are fully mixed with reaction material flow from an upper layer through fluid collecting, mixing and distributing equipment for heat exchange, are uniformly distributed and enter the next section of catalyst bed layer for continuous reaction, and reaction products after the reaction are discharged out of the reactor from a reaction product outlet at the bottom of the reaction zone.
A method for etherifying light gasoline includes such steps as filling at least two solid acid catalyst beds in reaction region, introducing the mixture of light gasoline and methanol to heat exchange region from top inlet, directly contacting with the vaporized steam from reaction region for heat exchange, contacting with catalyst, etherifying reaction of active olefin and methanol in light gasoline, introducing the other part of mixture of etherifying raw material to intermediate inlet, mixing with the reaction material from upper layer, heat exchanging, uniformly distributing, and discharging the gasoline from reactor.
In the light gasoline etherification method provided by the invention, the light gasoline refers to hydrocarbon distillate with the distillation range of 20-100 ℃, the mass content of active olefin is 10-60 wt%, and the active olefin refers to tertiary carbon olefin or tertiary carbon olefin and secondary carbon olefin.
In the light gasoline etherification method provided by the invention, the solid acid catalyst is a solid acid catalyst which has a catalytic effect on light gasoline etherification in the field. One or more selected from cation exchange resin, heteropoly acid or heteropoly acid supported catalyst and modified molecular sieve catalyst.
In the light gasoline etherification method provided by the invention, the etherification reaction conditions are that the temperature is 30-120 ℃, the preferred temperature is 40-90 ℃, the pressure is 0.1-2.0 MPa, the preferred pressure is 0.2-1.0 MPa, and the volume space velocity is 0.1h-1-5.0h-1Preferably 0.5h-1-3.0h-1The molar ratio of the alcohol to the olefin is 0.8 to 2.5, preferably 1.0 to 2.0.
The heat exchange type multiphase reactor and the application method provided by the invention are further described with reference to the drawings and the specific technical scheme, but the invention is not limited thereby.
Fig. 1 is a schematic structural diagram of a heat exchange type multiphase reactor, as shown in fig. 1, a reactor shell is divided into an upper heat exchange zone 3 and a lower reaction zone 2, and a top feeding port 1 and a gas phase outlet 6 are arranged at the top of the heat exchange zone. The heat exchange zone 3 is filled with filler or provided with a tower tray to provide a mass transfer and heat exchange surface required by vapor-liquid heat exchange. The reaction raw material is used for directly contacting and exchanging heat between an ascending vapor phase and the reaction raw material from the top feeding hole 1, the temperature of the reaction raw material is increased, the ascending vapor phase is partially condensed, the uncondensed vapor phase enters an external condenser 8 through a vapor phase discharging hole 6 and a control valve 7 to be cooled and then flows back, the backflow position can be positioned in the reaction area 2, and a heat exchange area backflow port 9 and a middle section feeding hole 10 of the reaction area can also be respectively arranged in the heat exchange area 3 and the reaction area 2. A plurality of sections of catalyst bed layers 5 are arranged in the reaction zone 2, and each section of catalyst bed layer can be filled with the same catalyst or different catalysts. A fluid collecting, mixing and distributing device 4 is arranged between the two catalyst bed layers, and a reaction product outlet 11 is arranged at the bottom of the reaction zone 2. The diameters of the heat exchange zone 3 and the reaction zone 2 are the same or different according to the vaporization quantity, and the diameter of the heat exchange zone 3 in the heat exchange type multiphase reactor in the attached figure 1 is smaller than that of the reaction zone.
In the heat exchange type multi-stage reactor provided by the invention, the inner components comprise a top inlet distributor which is optionally arranged at the top of the heat exchange zone 3 and a fluid collecting, mixing and distributing device between two sections of catalyst beds 5 in the reaction zone. If the heat exchange area adopts a filler type structural design, an inlet distribution disc, a bottom support disc and other related internal components are required to be arranged in the heat exchange area; the heat exchange area can also adopt the structural design of a common plate type tower tray.
Fig. 2 is a schematic structural view of a fluid collecting, mixing and distributing device. The fluid collecting, mixing and distributing device comprises a top support plate, a guide plate 12, an external fluid distribution pipe 13, a mixing chamber, a fluid distribution disc 16 and a bottom support plate 17 which are spaced from top to bottom, wherein the mixing chamber consists of an external annular primary mixing chamber 14 and a central secondary mixing chamber 15. The guide plate 16 is conical, and the cone angle is 140-175 degrees. The external fluid distribution pipe 13 is a circular ring-shaped pipeline and is communicated with the middle feed inlet 10 along the diameter direction of the reactor. The secondary mixing chamber 15 is formed by surrounding an inner layer and an outer layer of cylindrical barrels with openings, a guide plate at the top and a bottom plate with a circular opening in the middle, the diameter of the inner barrel is 1/3-3/4 of the diameter of the outer barrel, preferably 1/2-3/5, a plurality of rows and columns of openings which are the same or different in shape are arranged on the inner barrel and the outer barrel, and the openings can be in a circular, triangular, trapezoidal, spiral and other structures. The outer cylinder body open pore and the inner cylinder body open pore are arranged in a staggered order on the circumference. The pipe diameter of the external fluid distribution pipe 13 is 20-200mm, preferably 30-150mm, the diameter of the ring is larger than that of the outer cylinder of the secondary mixing chamber 15, round holes with phi 2-20mm are formed on the ring, and the distance between the holes is 10-200mm, preferably 20-100 mm.
The secondary mixing chamber 15 is preferably provided with staggered baffles, and the baffles can be rectangular, spiral, folded rectangular and the like, or wire mesh and corrugated packing to enhance mixing intensity. The top and bottom support plates 17 of the fluid collection, mixing and distribution device each employ a johnson mesh or wire mesh to support the solid catalyst bed and prevent catalyst loss.
The heat exchange type multiphase reactor provided by the invention is suitable for a gas-liquid-solid three-phase or liquid-solid two-phase reaction system with large heat release, and is particularly suitable for a solid catalytic reaction system in an exothermic reaction process with strong heat release or thermal mechanical equilibrium control. For example, the reaction system comprises etherification, esterification, hydrolysis, alkylation and other reaction processes controlled by thermodynamic equilibrium and a heat-releasing reaction process, wherein a solid catalyst is adopted in the reaction process, and the reaction materials are fed into a liquid phase or a gas-liquid two-phase.
The application method of the heat exchange type multiphase reactor provided by the invention comprises the following steps that reaction raw materials enter a heat exchange area 3 of the reactor from a top feeding hole 1 and are in direct contact heat exchange with vaporized components from a reaction area 2, the temperature of the raw materials is increased, the vaporized components are partially condensed, uncondensed gas-phase components enter a condenser 8 through a gas-phase outlet 6 after passing through a pressure control valve 7, the condensed materials enter the reaction area from a middle feeding hole 10 for further reaction, and meanwhile, the condensed materials can also return to the reactor from a return port 9 of the heat exchange area. After sufficient contact heat exchange, the reaction raw materials enter the reaction zone 2 to contact with the catalyst bed layer 5 for reaction. The reaction zone 2 is filled with a plurality of sections of catalyst bed layers, and the number of the bed layers is preferably 2-5; intermediate feed ports 10 are arranged between catalyst bed layers, and each intermediate feed port 10 is provided with a fluid collecting, mixing and distributing device 4.
The cooled reflux stream enters the reaction zone 2 through the intermediate feed inlet 10 and enters the preliminary mixing chamber 14 through the outer fluid distribution pipe 13. The upper fluid enters the preliminary mixing chamber 14 through the guide plate 12, and is primarily mixed and heat-exchanged with the return fluid entering from the external fluid distribution pipe 13 in the preliminary mixing chamber 14. The primarily mixed material flows through the opening on the outer cylinder body and enters the secondary mixing chamber 15 for further mixing. The secondary mixing chamber 15 is distributed with staggered baffles or wire mesh and corrugated packing to obtain higher mixing effect. The fluid after mixing and heat exchange enters the distribution disc 16 through a central circular hole on the bottom plate of the mixing chamber, and the fluid enters the next bed layer after being uniformly distributed for continuous reaction. The final reaction product is withdrawn from the reaction product outlet 11 at the bottom of the reactor.
The following examples and comparative examples illustrate the utility of the heat-exchange multiphase reactor provided by the present invention.
In the examples and comparative examples, light gasoline raw material 1 was cut from MIP full-range gasoline from Shijiazhuang oil refinery of China petrochemical Co., Ltd., final boiling point of light gasoline was 68 ℃, light gasoline raw material 2 was cut from MIO gasoline from Qilu Branch of China petrochemical Co., Ltd., final boiling point of light gasoline was 62 ℃, and main hydrocarbon composition was shown in Table 1. Methanol was commercially available as chemically pure. The component contents of the light gasoline feedstock and product were analyzed by gas chromatography. The olefin conversion was calculated using the change in olefin concentration at the reactor outlet and inlet.
Comparative example 1
Comparative example 1 etherification reaction of light gasoline with methanol was carried out using a conventional adiabatic fixed bed reactor. The height-diameter ratio of the reactor is 20, material flows enter from top to bottom, a side gap type inlet distributor is arranged at the inlet of the reactor, and the material flows in the reactor are naturally distributed. Wherein the mass fraction of tertiary carbon olefin with etherification activity is 24.7%, the feeding alcohol-olefin ratio is 1.05, the conventional commercial resin catalyst (D005-II, special resin Co., Ltd. of Dengganzhu) is adopted, and the feeding airspeed of fresh raw materials is 2.0h-1. The inlet temperature of the reactor is 55 ℃, and the reaction pressure is 0.5 MPa. The results of the etherification reaction are shown in Table 2.
Example 1
Example 1 a heat exchange multiphase reactor as shown in figure 1 was used, wherein the heat exchange zone was of packed construction and was internally provided with inlet distribution plates, bottom support plates and the like associated internals. The ratio of the heat exchange area to the reaction area is 0.6:1, and the height ratio is 0.2: 1. The reaction zone is filled with two sections of solid acid catalyst beds, the solid acid catalyst adopts commercial resin catalyst D005-II, the fluid collecting, mixing and distributing equipment is arranged between the two sections of catalyst beds, the structure of the fluid collecting, mixing and distributing equipment is shown in figure 2, the taper angle of the guide plate is 160 degrees, the diameter ratio of the inner cylinder body and the outer cylinder body of the secondary mixing chamber is 1/2, round holes which are arranged in a staggered mode are arranged on the inner cylinder body and the outer cylinder body, and the diameter of each round hole is 10 mm. Regular packing is filled in the secondary mixing chamber.
The etherification raw material and etherification catalyst are mixed as in comparative example 1, and the catalyst loading and fresh raw material treatment amount are the same as in comparative example 1. The mixed etherification raw materials are respectively added from a top feed inlet and a middle feed inlet, the flow ratio of the two is 2:1, and the mixed etherification raw materials are only added from the middle feed inlet of the reaction zone through cooling reflux. The inlet temperature of the top raw material is 55 ℃, and the reaction pressure is 0.25 MPa. The results of the etherification reaction are shown in Table 2.
Comparative example 2
Comparative example 2 etherification of light gasoline with methanol was carried out using a bubble point reactor as described in CN 200977456 a. The composition of the etherification raw material is shown in a light gasoline raw material 2 in Table 1, wherein the mass fraction of tertiary carbon olefin with etherification activity is 50.3%, the feeding alcohol-olefin ratio is 1.10, a conventional commercial resin catalyst (D005-II, Special resin Co., Ltd. of Deng Mingzhu) is adopted, and the feeding airspeed of the fresh raw material is 2.0h-1. The inlet temperature of the reactor is 50 ℃, and the reaction pressure is 0.35 MPa. The results of the etherification reaction are shown in Table 2.
Example 2
Example 2 a heat exchange multiphase reactor as shown in figure 1 was used, wherein the heat exchange zone was designed using a common plate tray configuration; two catalyst beds are arranged in the reaction zone, fluid collecting, mixing and distributing equipment is arranged between the two catalyst beds, and the diameter of the heat exchange zone is the same as that of the reaction zone. The guide plate cone angle is 160 degrees, and the secondary mixing chamber is indoor outer barrel diameter ratio is 1/3, all is equipped with staggered arrangement's circular port on the interior outer barrel, and circular port diameter 10 mm. The baffle inside the secondary mixing chamber adopts a spiral baffle as shown in figure 3. The ratio of the heat exchange area to the reaction area is 1:1, and the height ratio is 0.25: 1.
The composition of the mixed etherification raw material and the solid acid catalyst are the same as the comparative example 2, and the catalyst loading and the fresh raw material treatment amount are the same as the comparative example 2. The reaction flow is shown in figure 1, cooling reflux is respectively added from a reflux port 9 of the heat exchange zone and a middle feed port 10 of the reaction zone, and the flow ratio of the two streams is 1: 3. The top raw material inlet temperature of the reactor was 50 ℃ and the reaction pressure was 0.28 MPa. The results of the etherification reaction are shown in Table 2.
Table 1 light gasoline feedstock hydrocarbon composition wt%
Figure BDA0002245717590000111
TABLE 2
Figure BDA0002245717590000112

Claims (18)

1. A heat exchange type multiphase reactor comprises a reactor shell, a top feeding hole, a middle feeding hole, fluid collecting, mixing and distributing equipment, a top outlet and a reaction product outlet, wherein the reactor shell comprises an upper heat exchange area and a lower reaction area, the top feeding hole and the top outlet are arranged at the top of the heat exchange area, the heat exchange area is filled with filler or provided with a column plate, at least two catalyst bed layers are arranged in the reaction area, the middle feeding hole and the fluid collecting, mixing and distributing equipment are arranged on the catalyst bed layers, and the reaction product outlet is arranged at the bottom of the reaction area.
2. A heat-exchanging multiphase reactor according to claim 1, wherein an inlet distribution device is provided at the top of said heat exchange area, said inlet distribution device comprising an inlet distributor and an inlet distribution plate.
3. The heat-exchanging multiphase reactor according to claim 1 or 2, wherein the fluid collecting, mixing and distributing device comprises a top support plate, a guide plate, an outer fluid distribution pipe, a mixing chamber, a fluid distribution plate and a bottom support plate which are spaced from top to bottom, wherein the mixing chamber consists of an outer annular primary mixing chamber and a centrally located secondary mixing chamber; the external fluid distribution pipe is a circular or grid pipeline with small holes and is communicated with the middle feed inlet; the fluid distribution plate is provided with small holes.
4. A heat exchange multiphase reactor according to claim 3, wherein the baffle is a conical plate having a cone angle of 140 ° to 175 °.
5. A heat-exchanging multiphase reactor according to claim 3, wherein the secondary mixing chamber is surrounded by an inner and an outer layer of cylindrical barrels having openings, a top baffle, and a bottom plate having openings.
6. The heat-exchanging multiphase reactor according to claim 5, wherein the diameter of the cylinder in the secondary mixing chamber is 1/3-3/4 of the diameter of the outer cylinder.
7. A heat-exchanging multiphase reactor according to claim 5, wherein the openings of the inner and outer cylinders of the secondary mixing chamber are circumferentially arranged in a staggered order, the diameter of the openings of the outer cylinder being 5-50mm, preferably 6-30mm, and the diameter of the openings of the inner cylinder being 3-40mm, preferably 5-25 mm.
8. A heat exchange multiphase reactor according to claim 3, wherein the outer fluid distribution pipe is a circular ring pipe, the outer fluid distribution pipe has a pipe diameter of 20-200mm, and is provided with circular holes having a diameter of 2-20mm, and the distance between the holes is 10-200 mm.
9. The heat-exchanging multiphase reactor according to claim 8, wherein the outer fluid distribution pipe has a pipe diameter of 30-150mm, and the hole pitch of the circular holes is 20-100 mm.
10. A heat exchange multiphase reactor according to claim 3, wherein the secondary mixing chamber is internally provided with staggered baffles selected from rectangular, spiral, folded rectangular flat plates, wire mesh, corrugated packing.
11. A heat-exchanging multiphase reactor according to claim 1 or 2, wherein the ratio of the diameter of the heat-exchanging zone to the diameter of the reaction zone is (0.5-1.0): 1, the height ratio is (0.1-0.5): 1.
12. a heat-exchanging multiphase reactor according to claim 1 or 2, wherein said top outlet is connected to the upper part of the heat-exchanging zone and/or to the intermediate inlet of said reaction zone via a condenser cooler.
13. A method for using heat-exchanging multiphase reactor, which adopts the heat-exchanging multiphase reactor of any claim 1-12, the reaction zone is filled with at least two catalyst beds, one part of reaction raw material is introduced into the heat-exchanging zone from the top feeding port, and directly contacts with the reaction raw material steam from the reaction zone for heat exchange, then enters the reaction zone, contacts with the catalyst for exothermic reaction, the other part of reaction raw material is introduced from the middle feeding port, and is uniformly distributed to enter the next catalyst bed for continuous reaction after being fully mixed and heat exchanged with the reaction material flow from the upper layer through the fluid collecting, mixing and distributing device, and the reaction product after the reaction is finished is discharged out of the reactor from the reaction product outlet at the bottom of the reaction zone.
14. A light gasoline etherification method is characterized in that the heat exchange type multiphase reactor of claims 1-13 is adopted, at least two solid acid catalyst bed layers are filled in a reaction zone, one part of mixed etherification raw materials consisting of light gasoline and methanol is introduced into the heat exchange zone from a top feed inlet, is directly contacted with vaporized steam from the reaction zone for heat exchange, then enters the reaction zone, is contacted with a catalyst for etherification reaction of active olefin and methanol in the light gasoline under the etherification reaction condition, the other part of mixed etherification raw materials is introduced from a middle feed inlet, is fully mixed with reaction material flow from an upper layer by a fluid collecting, mixing and distributing device and is subjected to heat exchange, and then is uniformly distributed to enter the next catalyst bed layer for continuous reaction, and gasoline products after the etherification reaction are discharged out of the reactor from a reaction product outlet at the bottom of the reaction zone.
15. The light gasoline etherification method according to claim 14, wherein the liquid phase of the vapor at the top outlet of the heat exchange zone after cooling and condensation is returned to the reaction zone through the intermediate feed inlet.
16. The method for etherifying light gasoline as claimed in claim 14 or 15, wherein the light gasoline raw material is a hydrocarbon fraction having a distillation range of 20 ℃ to 100 ℃, and the tertiary carbon olefin content is 10% to 60% by mass.
17. The light gasoline etherification process according to claim 14 or 15, wherein the solid acid catalyst is selected from one or more of cation exchange resin, heteropoly acid or heteropoly acid-supported catalyst and modified molecular sieve catalyst; the etherification reaction conditions are as follows: the temperature is 30-120 ℃, the pressure is 0.1-2.0 MPa, and the volume space velocity is 0.1h-1-5.0h-1The molar ratio of the alcohol to the olefin is 0.8-2.5.
18. The light gasoline etherification process according to claim 17, wherein the etherification reaction conditions: the temperature is 40-90 ℃, the pressure is 0.2-1.0 MPa, and the volume space velocity is 0.5h-1-3.0h-1The molar ratio of alcohol to olefin is 1.0-2.0.
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