CN106111041A - A kind of continuous reaction apparatus and the method using this device synthesis furfurylmercaptan - Google Patents

A kind of continuous reaction apparatus and the method using this device synthesis furfurylmercaptan Download PDF

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CN106111041A
CN106111041A CN201610709249.9A CN201610709249A CN106111041A CN 106111041 A CN106111041 A CN 106111041A CN 201610709249 A CN201610709249 A CN 201610709249A CN 106111041 A CN106111041 A CN 106111041A
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reactor
advection
aqueous solution
thiourea
furfuryl
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CN106111041B (en
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宋成斌
卫洁
陈祥
臧传近
李新
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WUTONG AROMA CHEMICALS CO Ltd
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WUTONG AROMA CHEMICALS CO Ltd
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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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/245—Stationary reactors without moving elements inside placed in series
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2455—Stationary reactors without moving elements inside provoking a loop type movement of the reactants
    • B01J19/2465—Stationary reactors without moving elements inside provoking a loop type movement of the reactants externally, i.e. the mixture leaving the vessel and subsequently re-entering it
    • 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
    • B01J4/00—Feed or outlet devices; Feed or outlet control devices
    • B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • 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
    • B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
    • B01J2204/005—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the outlet side being of particular interest
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00002—Chemical plants
    • B01J2219/00027—Process aspects
    • B01J2219/00033—Continuous processes
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of continuous reaction apparatus and the method using this device synthesis furfurylmercaptan, this device includes mixed flow reactor and advection insulation reaction device；Wherein, described mixed flow reactor include shell and tube reactor, venturi mixer and with the low head being connected bottom described shell and tube reactor；Include several vertical ducts for material reaction inside described shell and tube reactor, have between described vertical duct and/or between described vertical duct and described tubular reaction wall and accommodate steam and/or the gap of cooling water；Described tubular reaction wall is provided with steam inlet, cooling water intake and condensation-water drain less；Described venturi mixer is connected with the vertical duct in described shell and tube reactor by described low head；Described advection insulation reaction wall is provided with several material outlets, and described advection insulation reaction device inside is connected with the vertical duct in described shell and tube reactor.Continuous conduit formula reactor in the present invention can be applicable to be suitable for the various product types of successive reaction, and the technique of such as furfurylmercaptan produces, and the high-efficiency and continuous that can realize furfurylmercaptan produces.

Description

Continuous reaction device and method for synthesizing furfurylthiol by adopting same
Technical Field
The invention relates to a continuous reaction device and a method for synthesizing furfuryl mercaptan by adopting the device.
Background
Furfuryl mercaptan, commonly known as cafaldehyde, is also called furfuryl mercaptan when it is called 2-thiofurancarbinol, and has the molecular formula: c5H6OS, structural formula:furfuryl mercaptan is a naturally occurring, internationally approved flavor for consumption. The american association of food flavor and extract manufacturers, international flavor and cosmetics agency, approved for its code: FEMA No 2493 is an important aroma component of roasted coffee, has coffee aroma and coconut smell, is widely used for blending coffee, chocolate and other aroma, can be used for soft drinks, ice cream, ice food, candy, baked food, jelly, pudding, frosting and the like, and is an important edible spice. The application is very wide, and the application is very mature and safe in food addition, such as: the dosage of the candy and baked food is 2 ppm. The dosage of soft drink, ice food and sugar frost is 0.5 ppm-0.78 ppm. The dosage of jelly and pudding is 0.1 ppm. The product quality is more than or equal to 99 percent.
The current synthetic routes of furfurylthiol mainly comprise three types: (l) The difurfuryl disulfide is prepared by reduction of zinc powder in an alcohol and acetic acid system, and the yield is about 73 percent; (2) the compound is prepared by reacting thiourea with furfuryl chloride, and the yield is about 33%; (3) prepared by reacting furfuryl alcohol with thiourea, and the yield is 55-60%. The third type is commonly used at present and is finished in a reaction kettle.
The existing synthesis device and method have the problems of higher product cost, lower yield, difficult control of reaction conditions and the like.
Disclosure of Invention
The invention aims to provide a continuous reaction device and a method for synthesizing furfuryl mercaptan by adopting the device, which overcome the problems of high product cost, low yield, difficult control of reaction conditions and the like in the prior art and realize high-efficiency continuous production of products.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first object of the invention is to provide a continuous reaction device, which comprises a mixed flow reactor and a advection heat preservation reactor;
the mixed flow reactor comprises a tubular reactor, a Venturi mixer and a lower end enclosure connected with the bottom of the tubular reactor; the interior of the shell and tube reactor comprises a plurality of vertical pipelines for material reaction, and gaps for containing steam and/or cooling water are arranged among the vertical pipelines and/or between the vertical pipelines and the shell and tube reactor wall; the wall of the tubular reactor is at least provided with a steam inlet, a cooling water inlet and a condensed water outlet; the Venturi mixer is communicated with the vertical pipeline in the tubular reactor through the lower end socket;
the wall of the advection heat-preservation reactor is provided with a plurality of material outlets, and the interior of the advection heat-preservation reactor is communicated with the vertical pipeline in the tubular reactor.
According to the design principle of the invention, the mixed flow reactor and the advection heat preservation reactor can be arranged up and down or left and right. However, when the reaction is continuous, the problems of energy saving and cost are fully considered, and the heat preservation reaction of the upper part is fully considered by utilizing the waste heat of the lower part during the design, therefore, the invention is preferably that the mixed flow reactor and the advection heat preservation reactor are arranged up and down; further preferably, the mixed flow reactor and the advection heat preservation reactor are integrated, and the mixed flow reactor and the advection heat preservation reactor are designed into an integrated reactor, so that the stability of system materials is facilitated. Tests prove that the mixed flow reactor and the advection heat preservation reactor can be arranged from left to right, but the mode of arranging the mixed flow reactor and the advection heat preservation reactor from top to bottom is not more energy-saving and effective.
Preferably, to realize three times of material baffling in the mixed flow reactor, the three times of baffling refers to three back and forth times of material in the vertical pipeline in the vertical stroke, a lower baffling cap of the vertical pipeline capable of sealing the peripheral annular part (described by the angle of the cross section of the tubular reactor) of the tubular reactor is arranged in the lower head, and an upper baffling cap of the vertical pipeline capable of sealing and removing the rest part of the peripheral annular part is arranged in the bottom of the horizontal flow heat preservation reactor or in the top of the tubular reactor. Specifically, the lower baffling cap is an annular head sealing structure (including an annular head sealing structure and a square annular head sealing structure) or a similar annular head sealing structure, and can seal a vertical pipeline of a peripheral annular part of the tubular reactor; the upper baffling cap is of an end enclosure structure and can seal and remove the vertical pipeline of the residual inner circular part of the peripheral annular part, and the upper baffling cap and the lower baffling cap are matched with each other to realize three times of material baffling in the mixed flow reactor. Furthermore, in order to realize multiple times of material baffling in the mixed flow reactor, the actual requirements can be further met by designing the structures of the upper baffling cap and the lower baffling cap. The design has the advantages of being beneficial to temperature control and energy saving.
Preferably, the shell and tube reactor wall is also provided with a vent.
Preferably, the upper part of the wall of the tubular reactor is provided with a steam inlet and an emptying vent, and the lower part of the wall of the tubular reactor is provided with a condensed water outlet and an emptying vent. The steam condensate outlet is designed to be higher than the common design position, and is used as the steam condensate outlet and the cooling water outlet.
Preferably, the advection heat preservation reactor is provided with three discharge ports from top to bottom in sequence. Further preferably, the three discharge ports are respectively arranged at the upper, middle and lower parts of the wall of the advection stabilizer. The three discharge ports are designed, the first discharge port is half of the discharge port and is used when the vehicle is just started, the middle discharge port is used with normal design yield, and the uppermost discharge port is overloaded or is reserved when the design does not meet the requirement.
Preferably, the length-diameter ratio (the ratio of the length to the diameter of each vertical pipeline) of the vertical pipelines is 45-55: 1, further preferably, the length-diameter ratio of the vertical pipeline is 50: 1.
preferably, according to the actual production requirement, a plurality of concentration meters, pH meters and thermometers are arranged on the continuous reaction device.
Preferably, each component of the continuous reaction apparatus is made of a corrosion-resistant material.
Preferably, the venturi mixer is further communicated with the interior of the advection heat preservation reactor, the materials are firstly mixed in the venturi mixer, when the materials pass through the venturi mixer, negative pressure is generated to suck part of the materials in the advection heat preservation reactor to participate in reaction, and the suction amount is controlled through a valve. The subtlety here is that the partial mixing of the reaction mass contributes to the forward direction of the reaction.
The venturi mixer of the present invention is a device capable of efficiently mixing materials, is a member conventionally available to those skilled in the art, is not particularly limited, and is commercially available.
The continuous reaction device is used for mixing materials and carrying out chemical reaction, the lower part of the device is a mixed flow reactor, and the device is provided with a vertical pipeline and a heating and cooling system (heating steam and cooling water are in a shell pass, the shell pass refers to a part contacted by a medium on the outer surface of the vertical pipeline, and the medium is the heating steam or the cooling water). The length-diameter ratio of the vertical pipeline is designed according to 50: 1. The upper part of the device is an advection heat preservation reactor which mainly plays a roleThe residence time of the materials is ensured to be sufficient, so that the product yield is high, the volume of the advection heat-preservation reactor is designed to be 2.8-4 h of the residence time of the system materials, and the residence time is preferably 3h in terms of product yield and cost, such as: total hourly material feed was given in units of 1 and the advection reactor was designed in units of 3 (for example: total material feed of 1 m)3The design of the advection heat-preservation reactor is 3m3) And evenly (or according to the yield) divided into three sections, respectively opened, designed with discharge ports, and discharged according to the reaction effect and the yield. The total material feeding amount refers to the total feeding amount of the four materials of the hydrochloric acid solution, the furfuryl alcohol, the thiourea aqueous solution and the sodium hydroxide aqueous solution.
The second purpose of the invention is to provide a process system for producing furfuryl mercaptan by continuous reaction, which at least comprises a continuous reaction device, a plurality of material tanks, a sodium hydroxide aqueous solution storage tank, a water vapor distiller, a condenser, a first laminator and a second laminator;
the material tank is connected with a Venturi mixer in the continuous reaction device;
a discharge port of an advection heat-preservation reactor in the continuous reaction device is connected with a liquid inlet of the steam distiller through a sodium hydroxide aqueous solution storage tank, and a liquid outlet of the steam distiller is connected with a liquid inlet of the first layering device; and a distillate outlet of the water vapor distiller is connected with a liquid inlet of the second delayer through a condenser.
Preferably, the continuous reaction production system further comprises a crude product storage tank, and the first delayer and the second delayer are further connected with the crude product storage tank, so that the oil phase in the first delayer and the second delayer enters the crude product storage tank.
And determining whether to add the unreacted materials into the reactor to continue reaction or prepare a hydrochloric acid solution according to the content of the unreacted materials in the water phase layers in the first layer separator and the second layer separator. Therefore, the bottom of the first layer separator and the bottom of the second layer separator are respectively connected with the lower seal head or the material tank, so that the water phase in the first layer separator and the water phase in the second layer separator enter the seal head or the material tank. And after the system is kept balanced, the first layer separator and the second layer separator can be respectively connected with sewage treatment equipment for sewage treatment.
Preferably, the material tank at least comprises a hydrochloric acid solution storage tank, a furfuryl alcohol storage tank and a thiourea aqueous solution storage tank.
Preferably, the material tank and the sodium hydroxide aqueous solution tank are connected with other components through a pump. All materials can be metered and conveyed through a pump, so that all the materials can be continuously fed and controlled, and the continuous production of the furfuryl mercaptan is realized.
The steam distiller of the invention has the function of directly leading to steam, and taking out and cooling required materials in liquid by using the steam. The condenser functions to convert the distillate (mainly comprising steam and furfuryl mercaptan) into a liquid. The function of the demixer is to separate the oil phase from the liquid phase. The steam still, condenser and delaminator are conventional industrial equipment in the art and are commercially available.
The continuous pipe-line reactor of the present invention can be applied to the production of various product types suitable for continuous reaction, such as furfuryl mercaptan.
A third object of the present invention is to provide the use of the above-mentioned device for the synthesis of furfuryl mercaptan.
The fourth purpose of the invention is to provide a method for synthesizing furfuryl mercaptan by using the continuous reaction device, which comprises the following steps:
(1) preparing raw materials: hydrochloric acid solution, furfuryl alcohol, thiourea aqueous solution and sodium hydroxide aqueous solution;
(2) the method comprises the following steps of (1) feeding a hydrochloric acid solution, a furfuryl alcohol and a thiourea aqueous solution into a vertical pipeline in the mixed flow reactor according to a set proportion, enabling the hydrochloric acid, the furfuryl alcohol and the thiourea to reach the temperature required by reaction through steam heating and/or cooling of cooling water, and enabling part of the hydrochloric acid, the furfuryl alcohol and the thiourea to react to generate furfuryl isothiourea;
(3) the mixture system in the step (2) enters the advection stabilizer, and hydrochloric acid, furfuryl alcohol and thiourea in the mixture system continuously react to obtain furfuryl isothiourea; when the liquid level in the advection stabilizer reaches a set position, discharging in an overflow mode, and then reacting with a sodium hydroxide aqueous solution to generate furfuryl mercaptan.
In the step (1), the mass concentration of the hydrochloric acid is 25-35%, and preferably, the mass concentration of the hydrochloric acid is 30%. The purity of the furfuryl alcohol is 99%. The thiourea aqueous solution is prepared from thiourea and water according to the mass ratio of 42:100, and mixing to obtain a saturated thiourea aqueous solution. The mass concentration of the sodium hydroxide aqueous solution is 15-25%, and preferably, the mass concentration of the sodium hydroxide aqueous solution is 20%.
In the step (2), the required temperature is 50-60 ℃, preferably, the temperature is 54-56 ℃.
In the step (2), the flow ratio of the hydrochloric acid solution, the furfuryl alcohol and the thiourea aqueous solution entering the mixer is 0.5:0.5 (0.2-0.5).
In the step (2), in order to further control the hydrochloric acid, the furfuryl alcohol and the thiourea to reach the temperature required by the reaction so as to obtain sufficient reaction and save energy consumption, the mixed materials are subjected to three times of baffling or multiple times of baffling back mixing in the tubular reactor.
In the step (3), after sodium hydroxide is added, the pH of the mixture system is 7.5-8.5, and the preferable pH is 8.
In the step (3), the residual concentration of hydrochloric acid in the reaction system is measured, and the feeding amount of hydrochloric acid is properly added or reduced as required.
Further, after furfuryl mercaptan is generated in the step (3), a reaction product in the advection heat-preservation reactor enters a water vapor distiller, a distillate enters a second demixer after being condensed, a first oil phase and a first water phase are separated, and the first oil phase enters a furfuryl mercaptan crude product tank.
In order to continuously carry out the reaction, the liquid level in the water vapor distiller needs to be kept at a set position, the bottom effluent liquid is separated into a second oil phase and a second water phase through a first layering device, and the second oil phase enters a crude furfurylthiol tank.
And combining the first oil phase and the second oil phase to obtain the crude product of the furfurylthiol.
One of the above technical solutions has the following beneficial effects:
(1) when the materials are pumped in the Venturi mixer in the continuous reaction device, a negative pressure cavity is generated, the negative pressure has the effect of sucking part of the materials in the system again, the sucked materials are mixed with the pumped materials, and meanwhile, the Venturi mixer has the effect of assisting catalytic reaction according to a chemical reaction mechanism.
The continuous reaction device of the invention mainly comprises two sections of assembled structures. The lower section of the reaction device is a mixing flow reactor which is provided with a plurality of back mixing processes and a heating and cooling system (the tubular reactor is provided with a steam inlet and a cooling water inlet), the heating and cooling system is a core design system, the system can enable the relevant raw materials to reach the reaction temperature through steam heating, but along with the heat release of the reaction, when the temperature rises to the temperature which can not be adjusted by closing the steam, the cooling water can be immediately started to cool, thereby ensuring the heat preservation of the relevant raw materials to keep the temperature at the required temperature. The upper section of the reaction device is an advection stable section, which is mainly a heat preservation stage of reaction, the reactor at the section mainly keeps continuous reaction, and when the reaction starts, a certain space is provided for continuous reaction due to the fact that stable reaction needs a period of time, and a plurality of discharge ports can be used for discharging materials according to the reaction condition and the production yield after the reaction is stable.
The continuous reaction device can realize continuous feeding and discharging of materials, and keep a certain temperature to ensure stable reaction. The device is suitable for various product types suitable for continuous reaction, and can ensure that the yield of the furfurylthiol reaches about 85 percent.
(2) According to the production process of the furfurylthiol, the invention also provides a system for producing the furfurylthiol through continuous reaction, the system comprises the continuous reaction device, and further comprises a water vapor distiller, a condenser, a first layering device, a second layering device and other structures, the continuous production of the furfurylthiol is realized through adopting the system, and compared with a system for producing the furfurylthiol through a reaction kettle in the prior art (the yield is only about 55-60 percent), the yield is obviously improved and can be as high as about 85 percent.
(3) The continuous reaction device and the system for producing the furfurylthiol by continuous reaction have the advantages of simple operation and low cost.
(4) In the invention, the problems of the price of the raw material for synthesizing the furfuryl mercaptan, the yield of the product, the simplicity and convenience of operation and the like are considered, a continuous reaction device is used, so that the reaction condition is easy to control (the temperature fluctuation is more stable), and the thiourea and the furfuryl alcohol are continuously reacted under the acidic condition. The improved method has low energy consumption, realizes continuous operation, ensures more stable product quality, and has yield of furfurylthiol over 85%.
Drawings
FIG. 1 is a schematic view of the structure of a continuous reaction apparatus of the present invention.
FIG. 2 is a schematic diagram showing the structure of a system for producing furfuryl mercaptan by a continuous reaction according to the present invention.
FIG. 3 is a schematic view of the baffle assembly of the present invention.
FIG. 4 is a schematic top view of the tubular reactor of the present invention.
Fig. 5 to 8 are schematic structural views of the lower baffling cap.
Wherein, 1, a lower end enclosure, 1-1, a lower end enclosure flange, 2, a Venturi mixer, 3, a tubular reactor, 3-1, a steam inlet, 3-2, a cooling water inlet, 3-3, a steam condensate outlet, 3-4, an emptying and emptying port, 3-5, a thermometer, 3-6, an upper flange of the tubular reactor, 3-7, a tubular reactor cylinder, 3-8, a lower flange of the tubular reactor, 4, an advection heat preservation reactor, 4-1, 4-2, 4-3, a discharge port, 4-4, an advection heat preservation reactor cylinder, 4-5, a lower flange of the advection heat preservation reactor, 5, a sodium hydroxide aqueous solution storage tank, 6, a furfuryl alcohol storage tank, 7, a thiourea solution storage tank, 8, a thiourea solution storage tank, 9, a hydrochloric acid storage tank, 10 and a steam distiller, 11. the system comprises a first layer separator, a condenser, a second layer separator, a crude product storage tank, an upper baffling cap, a lower baffling cap, a first annular area, a second annular area and a circular area, wherein the first layer separator is 12, the condenser is 13, the second layer separator is 14, the crude product storage tank is 15, the upper baffling cap is 16.
Detailed Description
The process of the present invention is further illustrated below with reference to examples, but the invention is not limited thereto.
Example 1
The continuous reaction apparatus of the present invention can be applied to various product types suitable for continuous reactions. This example provides a continuous reaction apparatus for preparing furfuryl mercaptan, as shown in fig. 1, comprising a mixed flow reactor and a advection heat-preservation reactor 4; wherein:
the mixed flow reactor comprises a tubular reactor 3, a Venturi mixer 2 and a lower seal head 1 connected with the bottom of the tubular reactor 3.
The interior of the tubular reactor 3 comprises a plurality of vertical pipelines for material reaction, and gaps for accommodating (or circulating) steam and/or cooling water are arranged among the vertical pipelines and between the vertical pipelines and the wall of the tubular reactor; the aspect ratio (ratio of length to diameter of the pipe) of the vertical pipe is 50: 1.
the inner wall of the vertical pipeline is provided with a plurality of components for baffling materials; the component for baffling the materials is a baffle plate. The baffles are longitudinally staggered on the inner wall of the vertical pipe, so that the baffles are baffled for three times or more in the mixed flow reactor. The design has the advantages of being beneficial to temperature control and energy saving.
A steam inlet 3-1 and an emptying drain port 3-4 are arranged at the upper part of the wall of the tubular reactor 3, and a cooling water inlet 3-2 and a steam condensate outlet 3-3 are arranged at the lower part of the wall of the tubular reactor 3; the steam condensate outlet 3-3 is designed to be higher than the general design position, and is used as a steam condensate outlet and a cooling water outlet.
The venturi mixer 2 is communicated with a vertical pipeline in the tubular reactor 3 through the lower seal head 1;
the wall of the advection heat-preservation reactor is provided with 3 material outlets 4-1, 4-2 and 4-3, and the three material outlets are respectively arranged at the upper, middle and lower parts of the wall of the advection stabilizer. The three discharge ports are designed, the first discharge port is half of the discharge port and is used when the vehicle is just started, the middle discharge port is used with normal design yield, and the uppermost discharge port is overloaded or is reserved when the design does not meet the requirement.
The problems of energy conservation and cost are fully considered while the reaction is continuous, and the heat preservation reaction at the upper part is completed by utilizing the waste heat of the heat at the lower part during the design, so the advection heat preservation reactor 4 is arranged at the top of the tubular reactor 3, namely the advection heat preservation reactor is arranged up and down. The interior of the advection heat-preservation reactor 4 is communicated with the vertical pipeline in the tubular reactor 3. During actual production, the tubular reactor 3 and the advection heat preservation reactor 4 can be designed into a whole, which is beneficial to the stability of system materials.
Further, according to the actual production requirement, a plurality of concentration meters, pH meters and thermometers are arranged on the continuous reaction device, and 3-5 in the figure 1 are thermometers.
Further, in order to increase the service life of the entire apparatus, each component of the continuous reaction apparatus is made of a corrosion-resistant material.
Further, the venturi mixer 2 is communicated with the inside of the advection heat preservation reactor 4, materials are firstly mixed in the venturi mixer 2, when the materials pass through the venturi mixer 2, negative pressure is generated to suck partial materials in the advection heat preservation reactor 2 to participate in reaction, and the suction amount is controlled through a valve. The subtlety here is that the partial mixing of the reaction mass contributes to the forward direction of the reaction.
Furthermore, according to the actual production requirement, the volume of the advection heat-preservation reactor is designed to be 3 hours of the retention time of the system materials. The residence time is illustrated by 3 h: the total material feeding amount per hour is 1 unit, and the advection heat-preservation reactor is designed to be 3 units (the total material feeding amount is 1 m)3The design of the advection heat-preservation reactor is 3m3/h)。
The yield of the furfurylthiol crude product prepared by the continuous reaction device is more than 85 percent.
Further, as shown in FIG. 3, the top of the tubular reactor 3 is connected to the horizontal flow heat-insulating reactor 4 through flanges (lower flanges 4-5 of the horizontal flow heat-insulating reactor and tubular reactors 3-6). The bottom of the tubular reactor 3 is connected with the lower seal head 1 through flanges (a lower flange 3-8 and a lower seal head flange 1-1 of the tubular reactor). Wherein, 3-7 are tubular reactor cylinders, and 4-4 are advection heat preservation reactor cylinders.
Furthermore, in order to realize the material baffling in the mixed flow reactor for three times, a lower baffling cap 16 is arranged in the lower end enclosure, the lower baffling cap 16 is of an annular end enclosure structure or is of a similar annular end enclosure structure, the structure forms are various, the structure can be as shown in fig. 5-8, the shape is not limited, the embodiment is preferably an annular seal head as shown in fig. 5, the annular seal head can seal the vertical pipelines of the annular part around the outer part of the tubular reactor 3 (as shown in fig. 4, a first annular area 17 and a second annular area 18), an upper baffling cap 15 is arranged in the bottom of the advection heat-preservation reactor 4 or the top of the tubular reactor 3, the upper baffling cap is a conventional head structure capable of sealing the vertical tubes of the inner circular portion of the shell-and-tube reactor 3 (as shown in fig. 4, the inner annular region includes a second annular region 18 and a circular region 19).
The process of three times of baffling of material liquid is realized: the mixed material liquid enters the tubular reactor 3 through the lower seal head 1, the tubular reactor is divided into three chambers under the action of the upper and lower baffling caps, the liquid firstly flows upwards from the middle into the tubular reactor 3 (the vertical pipeline of the circular area 19) through the lower baffling cap 16, then flows downwards into the tubular reactor 3 (the vertical pipeline of the second annular area 18) under the action of the upper baffling cap 15 after reaching the top of the tubular reactor 3, and then flows downwards into the horizontal flow heat preservation reactor 4 at the upper part from the outermost tubular reactor (the vertical pipeline of the first annular area 17).
Example 2
A system for producing furfuryl mercaptan by continuous reaction, as shown in fig. 2, at least comprising a continuous reaction device (as shown in fig. 1) described in example 1, a furfuryl alcohol storage tank 6, a thiourea preparation and dissolution storage tank 7, a thiourea solution storage tank 8, a hydrochloric acid storage tank 9, a sodium hydroxide aqueous solution storage tank 5, a steam distiller 10, a condenser 12, a first delayer 11, a second delayer 13 and a crude product storage tank 14;
the furfuryl alcohol storage tank 6, the thiourea preparing and dissolving storage tank 7, the thiourea solution storage tank 8 and the hydrochloric acid storage tank 9 are connected with the Venturi mixer 2 in the continuous reaction device through a pump and a pipeline;
a discharge port of an advection heat-preservation reactor 4 in the continuous reaction device is connected with a liquid inlet of the steam distiller 10 through a sodium hydroxide aqueous solution storage tank 5, and a liquid outlet of the steam distiller 10 is connected with a liquid inlet of a first layering device 11; the distillate outlet of the steam distiller 10 is connected with the liquid inlet of the second layer separator 13 through a condenser 12.
The upper parts of the first and second laminators 11 and 13 are also connected with a crude product storage tank 14, so that the oil phase obtained by separation in the first and second laminators 11 and 13 enters the crude product storage tank 14.
Whether to add the unreacted materials into the reactor for continuous reaction or prepare hydrochloric acid solution is determined according to the content of the unreacted materials in the water phase layers in the first delayer 11 and the second delayer 13. Therefore, the bottom of the first delayer 11 and the bottom of the second delayer 13 are respectively connected with the lower seal head 1 or a furfuryl alcohol storage tank 6, a thiourea preparation and dissolution storage tank 7, a thiourea solution storage tank 8, a hydrochloric acid storage tank 9 and other material tanks, so that the water phase in the first delayer 11 and the water phase in the second delayer 13 enter the lower seal head 1 or the material tanks. After the system is kept balanced, the first layer separator 11 and the second layer separator 13 can be respectively connected with sewage treatment equipment for sewage treatment.
Example 3
A method for synthesizing furfuryl mercaptan using the continuous reaction apparatus of example 1, comprising the steps of:
(1) preparing raw materials: hydrochloric acid solution with the mass concentration of 30%, furfuryl alcohol (the content is more than 99%), thiourea in mass ratio: and (3) preparing a saturated thiourea aqueous solution and a sodium hydroxide solution with the mass concentration of 20% by using the water-42: 100.
(2) The method comprises the following steps of (1) feeding a hydrochloric acid solution, a furfuryl alcohol and a thiourea aqueous solution into a vertical pipeline in a mixed flow reactor according to a set proportion, wherein the flow proportion of the hydrochloric acid solution, the furfuryl alcohol and the thiourea aqueous solution into the mixed flow reactor is 0.5:0.5 (0.2-0.5), heating by steam and/or cooling by cooling water to enable the hydrochloric acid, the furfuryl alcohol and the thiourea to reach a temperature of 54-56 ℃ required by reaction, and reacting part of the hydrochloric acid, the furfuryl alcohol and the thiourea to generate furfuryl isothiourea;
when steam is heated, steam enters through a steam inlet, and the furfuryl isothiourea generated by the reaction of the hydrochloric acid, the furfuryl alcohol and the thiourea is an exothermic reaction, so that when the temperature is higher than 56 ℃, the temperature needs to be reduced to reach a proper reaction temperature, and at the moment, cooling water is introduced through a cooling water inlet. The combination of steam heating and cooling water cooling is used, so that the temperature is kept at 54-56 ℃.
In order to facilitate the temperature control and energy conservation, the mixed materials are subjected to three times of baffling or multiple times of baffling back mixing in the tubular reactor.
(3) The mixture system in the step (2) enters the advection stabilizer, and hydrochloric acid, furfuryl alcohol and thiourea in the mixture system continuously react to obtain furfuryl isothiourea; when the liquid level in the advection stabilizer reaches a set position, discharging in an overflow mode, and then reacting with a sodium hydroxide aqueous solution to generate furfuryl mercaptan, wherein the pH value of a reaction system is kept at about 8.
Example 4
A method for continuously synthesizing furfurylthiol using the system of example 2, comprising the steps of:
1. preparing raw materials: a hydrochloric acid solution with the mass concentration of 30% is stored in a hydrochloric acid storage tank 9, furfuryl alcohol (the content is more than 99%), stored in a furfuryl alcohol storage tank 6 and thiourea preparation and dissolution storage tank 7 according to the mass ratio: preparing a saturated thiourea aqueous solution with water of 42:100, transferring and storing the saturated thiourea aqueous solution in a thiourea solution storage tank 8, and storing a sodium hydroxide solution with the mass concentration of 20% in a sodium hydroxide aqueous solution storage tank 5.
2. The continuous production process of the furfuryl mercaptan comprises the following steps:
(1) starting the hydrochloric acid metering pump, gradually opening the hydrochloric acid feed valve to 0.5M when the pressure is normal3Per hour hydrochloric acid is pumped in.
(2) After the flow is stable, steam is simultaneously introduced through a steam inlet 3-1 to heat the tubular reactor 3 to 55 +/-1 ℃, and the materials are stably fed to the bottom of the advection heat preservation reactor 4.
(3) Simultaneously starting thiourea and furfuryl alcohol metering pumps, gradually starting thiourea feed valves, and adjusting the flow to 0.5M3H is used as the reference value. Then the furfuryl alcohol feed valve was opened to adjust the flow to 0.23M3The feed was stabilized.
At this time, part of the hydrochloric acid, furfuryl alcohol and thiourea in the tubular reactor 3 react to generate furfuryl isothiourea.
When steam is heated, steam enters through a steam inlet, and the furfuryl isothiourea generated by the reaction of the hydrochloric acid, the furfuryl alcohol and the thiourea is an exothermic reaction, so that when the temperature is higher than 56 ℃, the temperature needs to be reduced to reach a proper reaction temperature, and at the moment, cooling water is introduced through the cooling water inlet 3-2. The combination of steam heating and cooling water cooling is used, so that the temperature is kept at 54-56 ℃.
In order to further better control the hydrochloric acid, the furfuryl alcohol and the thiourea to reach the temperature required by the reaction so as to obtain full reaction and save energy consumption, the mixed materials are baffled for three times or baffled for multiple times and back mixed in the tubular reactor.
(4) Detecting the content change of furfuryl mercaptan in the advection heat-preservation reactor 4 every 10 minutes, and properly adjusting the feeding amount of furfuryl alcohol according to the content condition to achieve the effect of complete reaction.
(5) And (3) measuring the residual concentration of the hydrochloric acid after reaction at a discharge outlet at the lower part of the advection heat-preservation reactor 4, and properly increasing and decreasing the feeding amount of the hydrochloric acid as required to be proper.
(6) When the liquid level in the advection stabilization reactor 4 reaches the discharge port at the lower part, the liquid enters a pipeline leading to the steam distiller 10 through an overflow discharge pipe connected with the discharge port 4-1, a sodium hydroxide solution pump is started, a sodium hydroxide solution is pumped in simultaneously to react with the furfuryl isothiourea to generate furfuryl mercaptan, the furfuryl mercaptan is neutralized in the pipeline until the pH value is about 8, and the furfuryl mercaptan enters the steam distiller 10.
(7) When the liquid level in the steam distiller 10 reaches 1/3, steam distillation is started, the temperature is controlled to be 90-98 ℃, steam is condensed by a condenser 12 and then enters a second demixer 13, the distillate is demixed, the upper oil phase enters a crude product storage tank 14, and the water phase is recycled for preparing the hydrochloric acid and thiourea aqueous solution.
(8) The bottom water liquid of the steam distiller passes through a position 1/3-2/3 of a liquid level board in a valve control tank, the bottom effluent (the material which is not vaporized and comes out from the bottom of the steam distiller) passes through a first layering device 11 to separate an oil phase and enters a crude product storage tank 14, and the water phase determines whether to add a reactor for continuous reaction or prepare a hydrochloric acid solution according to the contents of furfurylthiol and raw material components in the water phase. And after the system is kept balanced, discharging the water phase to a sewage treatment center for treatment. At this time, the crude furfurylthiol is in the crude product storage tank 14, and the yield is over 85%.
(9) In addition, in order to better help the forward direction of the reaction, the materials are firstly mixed in the Venturi mixer 2, when the materials pass through the Venturi mixer 2, negative pressure is generated to suck part of the materials in the advection heat preservation reactor 4 to participate in the reaction, and the suction amount is controlled by a valve.
Further, after the crude products in the crude product storage tank 14 reach a certain amount, the crude products are refined to obtain a finished product of furfuryl mercaptan, and the purity of the finished product of furfuryl mercaptan can reach more than 99%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A continuous reaction device is characterized in that: comprises a mixed flow reactor and an advection heat preservation reactor; wherein,
the mixed flow reactor comprises a tubular reactor, a Venturi mixer and a lower end enclosure connected with the bottom of the tubular reactor; the interior of the tubular reactor comprises a plurality of vertical pipelines for material reaction, and gaps for accommodating steam and/or cooling water are arranged among the vertical pipelines and/or between the vertical pipelines and the wall of the tubular reactor; the wall of the tubular reactor is at least provided with a steam inlet, a cooling water inlet and a condensed water outlet; the Venturi mixer is communicated with the vertical pipeline in the tubular reactor through the lower end socket;
the wall of the advection heat-preservation reactor is provided with a plurality of material outlets, and the interior of the advection heat-preservation reactor is communicated with the vertical pipeline in the tubular reactor.
2. The apparatus of claim 1, wherein: a lower baffling cap capable of sealing the vertical pipelines of the peripheral annular part of the tubular reactor is arranged in the lower end enclosure, and an upper baffling cap capable of sealing and removing the vertical pipelines of the rest part of the peripheral annular part is arranged in the bottom of the advection heat-preservation reactor or in the top of the tubular reactor; preferably, the lower baffling cap is of an annular end enclosure structure or a similar annular end enclosure structure, the upper baffling cap is of an end enclosure structure, and the upper baffling cap and the lower baffling cap are matched with each other to realize three times of material baffling in the mixed flow reactor.
3. The apparatus of claim 1, wherein: the mixed flow reactor and the advection heat preservation reactor are arranged up and down or left and right.
4. The apparatus of claim 1, wherein: the wall of the shell and tube reactor is also provided with an emptying vent; preferably, the Venturi mixer is also communicated with the interior of the advection heat-preservation reactor.
5. The apparatus of claim 1, wherein: the advection heat-preservation reactor is sequentially provided with three discharge ports from top to bottom; preferably, the three discharge ports are respectively arranged at the upper, middle and lower parts of the wall of the advection stabilizer; preferably, a plurality of concentration meters, pH meters and thermometers are arranged on the continuous reaction device; preferably, the length-diameter ratio of the vertical pipeline is 45-55: 1, further preferably, the length-diameter ratio of the vertical pipeline is 50: 1.
6. a process system for producing furfuryl mercaptan by continuous reaction is characterized in that: the continuous reaction device at least comprises a continuous reaction device as claimed in any one of claims 1 to 5, a plurality of material tanks, a sodium hydroxide aqueous solution storage tank, a water vapor distiller, a condenser, a first delayer and a second delayer;
the material tank is connected with a Venturi mixer in the continuous reaction device;
the discharge port of the advection heat-preservation reactor in the continuous reaction device is connected with the liquid inlet of the steam distiller through the sodium hydroxide aqueous solution storage tank, and the liquid outlet of the steam distiller is connected with the liquid inlet of the first layering device; and a distillate outlet of the water vapor distiller is connected with a liquid inlet of the second delayer through a condenser.
7. The process system of claim 6, wherein: the continuous reaction production system further comprises a crude product storage tank, and the first delayer and the second delayer are further connected with the crude product storage tank, so that oil phases in the first delayer and the second delayer enter the crude product storage tank.
8. A method for synthesizing furfuryl mercaptan by using the continuous reaction apparatus according to any one of claims 1 to 5, comprising the steps of:
(1) preparing raw materials: hydrochloric acid solution, furfuryl alcohol, thiourea aqueous solution and sodium hydroxide aqueous solution;
(2) the method comprises the following steps of (1) feeding a hydrochloric acid solution, a furfuryl alcohol and a thiourea aqueous solution into a vertical pipeline in the mixed flow reactor according to a set proportion, enabling the hydrochloric acid, the furfuryl alcohol and the thiourea to reach the temperature required by reaction through steam heating and/or cooling of cooling water, and enabling part of the hydrochloric acid, the furfuryl alcohol and the thiourea to react to generate furfuryl isothiourea;
(3) the mixture system in the step (2) enters the advection stabilizer, and hydrochloric acid, furfuryl alcohol and thiourea in the mixture system continuously react to obtain furfuryl isothiourea; when the liquid level in the advection stabilizer reaches a set position, discharging in an overflow mode, and then reacting with a sodium hydroxide aqueous solution to generate furfuryl mercaptan.
9. The method of claim 8, further comprising: in the step (1), the mass concentration of the hydrochloric acid is 25-35%, and preferably, the mass concentration of the hydrochloric acid is 30%; the purity of the furfuryl alcohol is 99%; the thiourea aqueous solution is prepared from thiourea and water according to the mass ratio of 42:100, mixing and preparing a saturated thiourea aqueous solution; the mass concentration of the sodium hydroxide aqueous solution is 15-25%, preferably, the mass concentration of the sodium hydroxide aqueous solution is 20%;
in the step (2), the required temperature is 50-60 ℃, preferably, the temperature is 54-56 ℃;
in the step (2), the flow ratio of the hydrochloric acid solution, the furfuryl alcohol and the thiourea aqueous solution entering the mixer is 0.5:0.5 (0.2-0.5);
in the step (2), the mixed materials are subjected to three times of baffling or multiple times of baffling back mixing in a tubular reactor;
in the step (3), after sodium hydroxide is added, the pH of the mixture system in the advection heat-preservation reactor is 7.5-8.5, and the preferable pH is 8.
10. The method of claim 8, further comprising: after furfuryl mercaptan is generated in the step (3), feeding a reaction product furfuryl mercaptan into a water vapor distiller, condensing distillate, feeding the distillate into a second layer separator, separating a first oil phase and a first water phase, and feeding the first oil phase into a furfuryl mercaptan crude product tank;
the liquid level in the water vapor distiller needs to be kept at a set position, a second oil phase and a second water phase are separated from a bottom liquid through a first layering device, and the second oil phase enters a crude furfurylthiol tank.
CN201610709249.9A 2016-08-23 2016-08-23 A kind of continuous reaction apparatus and the method using device synthesis furfurylmercaptan Expired - Fee Related CN106111041B (en)

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CN105268394A (en) * 2014-07-17 2016-01-27 中国石油化工股份有限公司 Liquid acid alkylation reactor and application method thereof
CN205903897U (en) * 2016-08-23 2017-01-25 滕州市悟通香料有限责任公司 Consecutive reaction device and contain process systems of device's production chaff mercaptan

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88100388A (en) * 1988-02-02 1988-11-23 中国科学院化工冶金研究所 Rare-earth oxalate oxidizing roasting technology and device
EP0995489A2 (en) * 1998-10-21 2000-04-26 Praxair Technology, Inc. Process for accelerating fast reactions using high intensity plug flow tubular reactors
US20080249261A1 (en) * 2007-04-06 2008-10-09 Jiansheng Ding Method of preparing polymethylene-polyphenyl-polyamine
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