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 PDFInfo
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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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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- 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
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- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
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- 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
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- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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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
Technical field
The present invention relates to a kind of continuous reaction apparatus and the method using this device synthesis furfurylmercaptan.
Background technology
Furfurylmercaptan, popular name coffee aldehyde, another name 2-thio-furan methanol is again furfuryl mercaptan, molecular formula: C5H6OS, structural formula
For:Furfurylmercaptan is naturally-occurring, and allows the spice eaten in the world.International fragrance essence with
The U.S. food spice of cosmetics mechanism and the approval of extract maker association, its numbering: FEMA No 2493. is Baked Coffee
Important fragrant composition, there is coffee aroma and Cortex cocois radicis breath, be widely used in the allotment fragrance such as coffee, chocolate, can be used for soft drink
Material, ice cream, ices, confection, baked goods, jelly and pudding, frosting etc., be a kind of important flavorant.Application
Widely, in food adds, highly developed and safety is applied, such as: confection and baked goods class consumption 2ppm.Soft drink,
Ices, frosting class consumption (0.5ppm)～(0.78ppm).Jelly and pudding consumption 0.1ppm.Product quality: content >=
99%.
The synthetic route of furfurylmercaptan mainly has three kinds at present: (l) is used zinc by difurfuryl disulbide in ethanol and acetic acid
Powder reduction preparation, productivity about 73%；(2) preparation, productivity about 33% are reacted by thiourea and furfuryl chloride；(3) by furfuryl alcohol and sulfur
Urea reaction preparation, productivity 55%～60%.The most conventional is the third, completes in a kettle..
The problems such as it is higher that existing synthesizer and method exist product cost, and yield is on the low side, reaction condition is wayward.
Summary of the invention
It is an object of the invention to provide a kind of continuous reaction apparatus and the method using this device synthesis furfurylmercaptan, overcome
The problems such as in prior art, product cost is higher, and yield is on the low side, reaction condition is wayward, it is achieved the high-efficiency and continuous of product is raw
Produce.
For achieving the above object, the present invention is by the following technical solutions:
First purpose of the present invention is to provide a kind of continuous reaction apparatus, including mixed flow reactor and advection insulation reaction
Device；
Wherein, described mixed flow reactor include shell and tube reactor, venturi mixer and with described shell and tube reactor
The low head that bottom is connected；Include some vertical ducts for material reaction inside described shell and tube reactor, described vertically
Have between pipeline and/or between described vertical duct and described tubular reaction wall between receiving steam and/or cooling water
Gap；Described tubular reaction wall is provided with steam inlet, cooling water intake and condensation-water drain less；Described venturi mixes
Clutch 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 internal with
Vertical duct in described shell and tube reactor is connected.
Can be to be arranged above and below according to the design principle of the present invention, mixed flow reactor and advection insulation reaction device, it is also possible to
For left-right situs.But considering reaction continuous print simultaneously, taking into full account energy-conservation and cost problem, taking into full account when design
The waste heat utilizing bottom heat completes the insulation reaction on top, and therefore, the present invention is preferably, and described mixed flow reactor and advection are protected
Temperature reactor is for being arranged above and below, and the continuous reaction apparatus of the present invention is mainly by reaction and two mistakes of insulation on top of bottom
Cheng Shixian, top is to need to maintain certain temperature, and the form that this structure is designed as being arranged above and below contributes to the flat of top
Stream stablizes the insulation of reactor, utilizes the waste heat in mixed flow reactor to complete the insulation on top；It is further preferred that described mixed flow
Reactor and advection insulation reaction device are an entirety, are designed to an integral reactor, and beneficially system material is steady
Fixed.Through verification experimental verification, described mixed flow reactor and advection insulation reaction device can left-right situs, but not as the side being arranged above and below
Formula is more energy-conservation and effective.
Preferably, for realizing material baffling in mixed flow reactor three times, baffling refers to the material in vertical duct for three times
Three in its vertical stroke come and go back and forth, are provided with the surrounding's ring that can seal described shell and tube reactor in described low head
The lower baffling cap of the vertical duct of shape part (describing with the angle of the cross section of shell and tube reactor), the insulation of described advection is anti-
It is provided with in answering the bottom of device or in the top of shell and tube reactor and can seal the remainder removing described peripheral annular portion
The upper baffling cap of vertical duct.Concrete, described lower baffling cap be a ring-type end enclosure structure (include circular end enclosure structure and
Fang Huanzhuan end enclosure structure) or ring-like end enclosure structure, it is possible to seal peripheral annular portion perpendicular of described shell and tube reactor
To pipeline；Upper baffling cap is an end enclosure structure, it is possible to seal the residue inner circle part of the described peripheral annular portion of removing
Vertical duct, described upper baffling cap and lower baffling cap cooperate the material baffling that realizes in mixed flow reactor three times.Further
, for realizing material baffling in mixed flow reactor repeatedly, can meet reality by the structure designing upper and lower baffling cap further
Border demand.Advantage of this design is advantageous for the control of temperature and energy-conservation.
Preferably, described tubular reaction wall is additionally provided with emptying evacuation port.
Preferably, described tubular reaction wall top is provided with steam inlet and emptying evacuation port, and bottom is provided with condensed water
Outlet and emptying evacuation port.The position of steam condensate (SC) exit design is higher than general design attitude, both condenses with for steam
Water out with as coolant outlet.
Preferably, described advection insulation reaction device is sequentially provided with three discharging openings from top to bottom.It is further preferred that it is described
Three discharging openings are separately positioned on advection and stablize the position, upper, middle and lower of wall.It is to consider production problems and amplifying effect herein
Should design, not necessarily reach due to reaction effect to design requirement, cause unsuccessful, so, the present invention devises three and goes out
Material mouth, first discharging opening is to use when half yield and just driving, and middle discharging opening is that normal design yield uses,
Discharging opening above is over loading or design does not reaches when requiring standby.
Preferably, the draw ratio (length of every vertical duct and the ratio of diameter) of described vertical duct is 45～55:
1, it is further preferred that the draw ratio of described vertical duct is 50:1.
Preferably, according to actual production demand, described continuous reaction apparatus is provided with several densitometers, pH meter and temperature
Meter.
Preferably, all parts in described continuous reaction apparatus is made up of resistant material.
Preferably, described venturi mixer is also connected with inside advection insulation reaction device, and material is first at venturi
Blender mixes, and when material is by venturi mixer, produces negative pressure and the partial material in advection insulation reaction device is inhaled
Enter, participate in reaction, by Valve controlling suction volume.Ingenious place herein is to be to be mixed with the material parts of reaction to help instead
The positive direction answered is carried out.
Venturi mixer of the present invention is a kind of equipment that material high-efficiency can be made to mix, and it is art technology
The parts that personnel can conventional obtain, are not particularly limited, can be commercially available by commercial sources.
The effect of continuous reaction apparatus of the present invention is mixed material and carries out chemical reaction, and device bottom is mixed flow
Reactor, (for adding vapours and cooling water in shell side, shell side refers to vertical duct appearance vertical duct and heating and cooling system
The part that face medium is contacted, medium is for adding vapours or cooling water herein).Vertical duct draw ratio presses 50:1 design.Device
Top is advection insulation reaction device, and Main Function is to ensure that the time of material stop is more abundant so that product yield is higher, flat
Stream insulation reaction body amasss the time of staying 2.8h～4h being designed as system material, considers from product yield and cost,
Being preferably 3h, such as: material total feed is unit 1 per hour, advection insulation reaction device is designed as unit 3 and (illustrates: thing
Material total feed is 1m3/ h, advection insulation reaction device is designed as 3m3), and averagely (or according to yield) is divided into three sections, opens respectively
Mouthful, design discharging opening, by reaction effect and yield discharging.Described material total feed refers to that hydrochloric acid solution, furfuryl alcohol, thiourea are water-soluble
The these four material total feed of liquid and sodium hydrate aqueous solution.
Second object of the present invention is to provide a kind of successive reaction and produces the process system of furfurylmercaptan, at least includes described
Continuous reaction apparatus, several material pots, sodium hydrate aqueous solution storage tank, steam distillation device, condenser, first layer device and
Second quantizer；
Described material pot connects the venturi mixer in described continuous reaction apparatus；
The discharging opening of the advection insulation reaction device in described continuous reaction apparatus is connected by sodium hydrate aqueous solution storage tank
The inlet of described steam distillation device, the liquid outlet of described steam distillation device is connected with the inlet of first layer device；
The distillate outlet of described steam distillation device is connected by the inlet of condenser with described second quantizer.
Preferably, described successive reaction production system also includes crude product storage tank, described first layer device and the second quantizer
Also it is connected with crude product storage tank, makes the oil phase in first layer device and the second quantizer enter in crude product storage tank.
Content according to the unreacted material in the aqueous layer in first layer device and the second quantizer determines whether to add again
Enter and reactor continues reaction or deallocation salt manufacturing acid solution.Therefore, the bottom of described first layer device and the bottom of the second quantizer
It is connected with described low head or material pot the most respectively, makes the aqueous phase in first layer device and the second quantizer enter end socket or thing
In batch can.After keeping system balancing, described first layer device and the second quantizer also can connect sewage disposal device respectively, enter
Row sewage disposal.
Preferably, described material pot at least includes hydrochloric acid solution storage tank, furfuryl alcohol storage tank, thiourea solution storage tank.
Preferably, described material pot is connected with miscellaneous part by pump with sodium hydrate aqueous solution tank.All materials are equal
Can be measured by pump and carry, the most all of material can realize continuous feed and control, it is achieved furfurylmercaptan
Produce continuously.
The effect of the vapor distillation device in the present invention is by leading directly to steam, utilizes steam needing in liquid
Material web out cools down and obtains.The effect of condenser is that distillate (mainly including steam and furfurylmercaptan) is transformed into liquid.Point
The effect of layer device is oil phase and liquid phase to be separated.Described vapor distillation device, condenser and quantizer are that this area is conventional
Industrial equipment, can be commercially available by commercial sources.
Continuous conduit formula reactor in the present invention can be applicable to be suitable for the various product types of successive reaction, such as bran sulfur
The technique of alcohol produces.
Third object of the present invention is to provide the application in synthesis furfurylmercaptan of a kind of said apparatus.
Fourth object of the present invention is to provide a kind of method using above-mentioned continuous reaction apparatus synthesis furfurylmercaptan, including
Following steps:
(1) raw material is prepared: hydrochloric acid solution, furfuryl alcohol, thiourea solution and sodium hydrate aqueous solution；
(2) by hydrochloric acid solution, furfuryl alcohol and thiourea solution according to the ratio of setting enter in described mixed flow reactor vertical
In pipeline, heated by steam and/or cool down the cooling effect of water and make hydrochloric acid, furfuryl alcohol and thiourea reach to react temperature required,
And part hydrochloric acid, furfuryl alcohol and thiourea react and generate furfuryl group isothiourea；
(3) during the mixture system in step (2) enters described advection regulator, hydrochloric acid, bran in described mixture system
Alcohol and thiourea continue to react and obtain furfuryl group isothiourea；Overflow is passed through when the liquid level in advection regulator reaches setting position
Form discharging, then reacts generation furfurylmercaptan with sodium hydrate aqueous solution.
In step (1), the mass concentration of described hydrochloric acid is 25～35%, it is preferred that the mass concentration of described hydrochloric acid is
30%.The purity of described furfuryl alcohol is 99%.Described thiourea solution is that thiourea and water are according to mass ratio 42:100 mixed configuration
Saturated thiourea solution.The mass concentration of described sodium hydrate aqueous solution is 15～25%, it is preferred that described hydroxide
The mass concentration of sodium water solution is 20%.
In step (2), temperature required is 50～60 DEG C, it is preferred that described temperature is 54～56 DEG C.
In step (2), the flow proportional that described hydrochloric acid solution, furfuryl alcohol and thiourea solution enter in described flow mixing device is
0.5:0.5:(0.2～0.5).
In step (2), reach to react temperature required to obtain fully for better controling over hydrochloric acid, furfuryl alcohol and thiourea further
Reaction and energy efficient, mixed material carries out three bafflings or repeatedly baffling back-mixing in shell and tube reactor.
In step (3), after adding sodium hydroxide so that the pH of mixture system is 7.5～8.5, and preferred pH is 8.
In step (3), measure the hydrochloric acid residual concentration in reaction system, be properly added as required or reduce entering of hydrochloric acid
Doses reaches suitable.
Further, after step (3) generates furfurylmercaptan, in described advection insulation reaction device, product enters water vapour
In distillator, entering the second quantizer after distillate condensation, isolate the first oil phase and the first aqueous phase, the first oil phase enters bran sulfur
In alcohol crude product tank.
In order to make reaction be carried out continuously, the liquid level in steam distillation device need to be maintained at setting position, and the end goes out liquid through first
Quantizer isolates the second oil phase and the second aqueous phase, and the second oil phase enters furfurylmercaptan crude product tank.
Described first oil phase and the merging of the second oil phase are furfurylmercaptan crude product.
A technical scheme in technique scheme has the advantages that
(1) venturi mixer in the continuous reaction apparatus of the present invention, product pump is fashionable, produces negative pressure cavity, has negative pressure
Effect partial material in system resorbed, the material of suction mixes with the material pumped into, meanwhile, anti-according to chemistry
Mechanism is answered to help the effect of catalytic reaction.
The continuous reaction apparatus of the present invention is mainly made up of two sections of modular constructions.The hypomere of described reaction unit is mixed flow
Reactor, (above-mentioned shell and tube reactor is provided with steam inlet and cooling to have several back-mixing flow processs and heating and cooling system
Water water inlet), the heating and cooling system in the present invention is a core design system, and this system can make phase by steam heating
Close raw material and reach reaction temperature, but along with the heat release of reaction, when temperature rises to be regulated by steam off, Ke Yili
I.e. open cooling water temperature, thus it is temperature required to ensure that the insulation of related raw material keeps it in.The epimere of described reaction unit
For advection stable section, the mainly holding stage of reaction, this section of reactor is mainly maintenance reaction, mainly opens in reaction
During the beginning, owing to stable reaction needs a period of time, so there being certain space to continue reaction, when can basis after stable reaction
Response situation and production yields use multiple discharge hole for discharge.
By the continuous reaction apparatus of the present invention, it is possible to achieve the continuous feed of material and discharging, keep certain temperature
Stable reaction is made to react.This device is suitable for the various product types of successive reaction, can make the yield of furfurylmercaptan up to
About 85%.
(2) according to the production technology of furfurylmercaptan, present invention also offers a kind of successive reaction and produce the system of furfurylmercaptan, should
System includes described continuous reaction apparatus, also includes steam distillation device, condenser, first layer device and the second quantizer etc.
Structure, uses said system, it is achieved the continuous production of furfurylmercaptan, with the system that reactor of the prior art produces furfurylmercaptan
(productivity is only 55～about 60%), productivity significantly improves, and may be up to about 85%.
(3) simple to operate, the low cost of the system of the continuous reaction apparatus in the present invention and successive reaction production furfurylmercaptan.
(4) present invention is in view of synthesis furfurylmercaptan cost of material, the yield of product, the problem such as simplicity of operation, uses
Continuous reaction apparatus so that easy control of reaction conditions (temperature fluctuation is more stable), by thiourea and furfuryl alcohol in acidity
Under the conditions of carry out successive reaction.The power consumption of this improved method is few, it is achieved continuous operation ensure that product quality is more stable, generates furfurylmercaptan
Productivity can reach more than 85%.
Accompanying drawing explanation
Fig. 1 is the structural representation of the continuous reaction apparatus of the present invention.
Fig. 2 is the system structure schematic diagram that successive reaction of the present invention produces furfurylmercaptan.
Fig. 3 is the structural representation of baffling parts of the present invention.
Fig. 4 is the plan structure schematic diagram of shell and tube reactor in the present invention.
Fig. 5～Fig. 8 is the structural representation of lower baffling cap.
Wherein, 1, low head, 1-1, low head flange, 2, venturi mixer, 3, shell and tube reactor, 3-1, steam enter
Mouthful, 3-2, cooling water intake, the outlet of 3-3, steam condensate (SC), 3-4, emptying evacuation port, 3-5, thermometer, 3-6, shell and tube are anti-
Answer device upper flange, 3-7, shell and tube reactor cylinder, 3-8, shell and tube reactor lower flange, 4, advection insulation reaction device, 4-1,
4-2,4-3, discharging opening, 4-4, advection insulation reaction device cylinder, 4-5, advection thermophore lower flange, 5, sodium hydrate aqueous solution storage
Tank, 6, furfuryl alcohol storage tank, 7, the molten storage tank of thiourea system, 8, thiourea solution storage tank, 9, hydrochloric acid tank, 10, vapor distillation device, 11,
One quantizer, 12, condenser, the 13, second quantizer, 14, crude product storage tank, 15, upper baffling cap, 16, lower baffling cap, 17, first
Annulus, the 18, second annulus, 19, circle.
Detailed description of the invention
Below in conjunction with embodiment, the method for the present invention is illustrated further, but not thereby limiting the invention.
Embodiment 1
The continuous reaction apparatus of the present invention can be applicable to be suitable for the various product types of successive reaction.The present embodiment provides one
Plant the continuous reaction apparatus preparing furfurylmercaptan, as it is shown in figure 1, include mixed flow reactor and advection insulation reaction device 4；Wherein:
Described mixed flow reactor include shell and tube reactor 3, venturi mixer 2 and with described shell and tube reactor 3 end
The low head 1 that portion is connected.
Described shell and tube reactor 3 is internal includes several vertical ducts for material reaction, described vertical duct it
Between and described vertical duct and described tubular reaction wall between tool accommodate (or circulation) steam and/or the gap of cooling water；
The draw ratio (length of pipeline and the ratio of diameter) of described vertical duct is 50:1.
Several parts making material baffling are set on described vertical duct inwall；The described parts making material baffling are folding
Stream plate.Described deflection plate is positioned on vertical duct inwall along longitudinally staggered so that baffling three times or repeatedly in mixed flow reactor.
Advantage of this design is advantageous for the control of temperature and energy-conservation.
Described shell and tube reactor 3 wall top is provided with steam inlet 3-1 and emptying evacuation port 3-4, described tubular reaction
Device 3 wall bottom cooling water intake 3-2 and steam condensate (SC) outlet 3-3；The position ratio of steam condensate (SC) outlet 3-3 design is general
Design attitude want height, both with for steam condensate (SC) outlet and as coolant outlet.
Described venturi mixer 2 is connected with the vertical duct in described shell and tube reactor 3 by described low head 1
Logical；
Described advection insulation reaction wall is provided with 3 material outlets 4-1,4-2,4-3, and described three discharging openings set respectively
Put the position, upper, middle and lower stablizing wall at advection.Herein in order to consider that production problems and enlarge-effect design, due to
Reaction effect not necessarily reaches to design requirement, causes unsuccessful, so, the present invention devises three discharging openings, first discharging
Mouth is to use when half yield and just driving, and the discharging opening of centre is that normal design yield uses, and uppermost discharging opening is
Over loading or design do not reach when requiring standby.
Consider reaction continuous print simultaneously, take into full account energy-conservation and cost problem, take into full account when design and utilize bottom
The waste heat of heat completes the insulation reaction on top, therefore the top of described shell and tube reactor 3 arranges described advection insulation reaction device
4, it is the layout that is arranged above and below.Described advection insulation reaction device 4 is internal to be connected with the vertical duct in described shell and tube reactor 3
Logical.When actual production, shell and tube reactor 3 and advection insulation reaction device 4 can be designed as an entirety, beneficially system thing
Stablizing of material.
Further, according to actual production demand, described continuous reaction apparatus is provided with several densitometers, pH meter and temperature
Degree meter, in Fig. 1,3-5 is thermometer.
Further, in order to improve the service life of whole device, all parts in described continuous reaction apparatus is by resistance to
Corrosion material is made.
Further, described venturi mixer 2 is also internal with advection insulation reaction device 4 to be connected, and material is first at literary composition
In mound, blender 2 mixes, and when material is by venturi mixer 2, produces negative pressure by the part in advection insulation reaction device 2
Material sucks, and participates in reaction, by Valve controlling suction volume.Ingenious place herein is to be to be mixed with the material parts of reaction
The positive direction helping reaction is carried out.
Further, according to needs of production, when the volume of advection insulation reaction device is designed as the stop of system material
Between 3h.Illustrate time of staying 3h: material total feed is unit 1 per hour, and advection insulation reaction device is designed as unit 3
(material total feed is 1m3/ h, advection insulation reaction device is designed as 3m3/h)。
Using the furfurylmercaptan crude product that this continuous reaction apparatus prepares, productivity is more than 85%.
Further, as it is shown on figure 3, the top of shell and tube reactor 3 is by flange (advection insulation reaction device lower flange 4-
5 with shell and tube reactor 3-6) be connected with advection insulation reaction device 4.By flange, (shell and tube is anti-in the bottom of shell and tube reactor 3
Answer device lower flange 3-8 and low head flange 1-1) it is connected with low head 1.Wherein, 3-7 is shell and tube reactor cylinder, and 4-4 is flat
Stream insulation reaction device cylinder.
Further, for realizing material baffling in mixed flow reactor three times, in described low head, it is provided with lower baffling cap 16,
Lower baffling cap 16 is a ring-type end enclosure structure or in ring-like end enclosure structure, its version has multiple, can be such as Fig. 5～
Structure shown in 8, its shape is not particularly limited, and the present embodiment annular seal head the most as shown in Figure 5, ring-type end socket can
Seal vertical duct (as shown in Figure 4, the first annular district 17 and of the exterior circumferential annular section of described shell and tube reactor 3
Second ring district 18), it is provided with baffling cap 15 in the bottom of described advection insulation reaction device 4 or in the top of shell and tube reactor 3,
Described upper baffling cap is a conventional end enclosure structure, it is possible to seal the vertical duct of the inner circle part of described shell and tube reactor 3
Road (as shown in Figure 4, described inner annular district includes the second annulus 18 and circle 19).
Realize the process of three bafflings of feed liquid: mixed material liquid is to enter shell and tube reactor by low head 1
3, it is divided into three rooms, liquid to first pass through lower baffling cap 16 and flow upwardly into tubulation from centre tubulation by the effect of upper and lower baffling cap
Formula reactor 3 (vertical duct of circle 19), downward due to the effect of upper baffling cap 15 behind arrival shell and tube reactor 3 top
Being deflected into shell and tube reactor 3 (vertical duct of the second annulus 18), baffling is from outmost tubulation (the first ring the most again
The vertical duct in shape district 17) by finally entering the advection insulation reaction device 4 on top.
Embodiment 2
A kind of successive reaction produces the system of furfurylmercaptan, as in figure 2 it is shown, at least include successive reaction dress described in embodiment 1
Put (as shown in Figure 1), furfuryl alcohol storage tank 6, the molten storage tank of thiourea system 7, thiourea solution storage tank 8, hydrochloric acid tank 9, sodium hydrate aqueous solution
Storage tank 5, steam distillation device 10, condenser 12, first layer device the 11, second quantizer 13 and crude product storage tank 14；
Described furfuryl alcohol storage tank 6, the molten storage tank of thiourea system 7, thiourea solution storage tank 8, hydrochloric acid tank 9 connect institute by pump and pipeline
State the venturi mixer 2 in continuous reaction apparatus；
The discharging opening of the advection insulation reaction device 4 in described continuous reaction apparatus is by sodium hydrate aqueous solution storage tank 5 even
Connect the inlet of described steam distillation device 10, the liquid outlet of described steam distillation device 10 and the inlet of first layer device 11
It is connected；The distillate outlet of the described steam distillation device 10 inlet phase by condenser 12 with described second quantizer 13
Connect.
Described first layer device 11 is also connected with crude product storage tank 14 with the top of the second quantizer 13, makes first layer device
The oil phase of 11 and second isolateds in quantizer 13 enters in crude product storage tank 14.
Content according to the unreacted material in the aqueous layer in first layer device 11 and the second quantizer 13 determines whether
Add and reactor continues reaction or deallocation salt manufacturing acid solution.Therefore, the bottom of described first layer device 11 and the second quantizer
The bottom of 13 the most respectively with described low head 1 or furfuryl alcohol storage tank 6, the molten storage tank of thiourea system 7, thiourea solution storage tank 8, hydrochloric acid tank 9
It is connected Deng material pot, makes the aqueous phase in first layer device 11 and the second quantizer 13 enter in low head 1 or material pot.Work as guarantor
After holding system balancing, described first layer device 11 and the second quantizer 13 also can connect sewage disposal device respectively, carry out sewage
Process.
Embodiment 3
A kind of method of continuous reaction apparatus synthesis furfurylmercaptan used in embodiment 1, comprises the following steps:
(1) raw material is prepared: mass concentration is hydrochloric acid solution, the furfuryl alcohol (content > 99%), in mass ratio thiourea of 30%: water
=42:100 is configured to saturated thiourea solution, mass concentration is the sodium hydroxide solution of 20%.
(2) by hydrochloric acid solution, furfuryl alcohol and thiourea solution according to the ratio of setting enter in described mixed flow reactor vertical
In pipeline, the flow proportional that described hydrochloric acid solution, furfuryl alcohol and thiourea solution enter in described flow mixing device is 0.5:0.5:(0.2
～0.5), heated by steam and/or cool down the cooling effect of water and make hydrochloric acid, furfuryl alcohol and thiourea reach to react temperature required 54
～56 DEG C, and part hydrochloric acid, furfuryl alcohol and thiourea react generation furfuryl group isothiourea；
During steam heating, steam is entered by steam inlet, owing to the reaction of hydrochloric acid, furfuryl alcohol and thiourea generates furfuryl group isothiourea
For exothermic reaction, so when temperature is higher than 56 DEG C, needing cooling to reach suitable reaction temperature, now, by cooling
Water water inlet is passed through cooling water.Steam heating and cooling water cooling with the use of so that temperature is maintained at 54～56 DEG C.
For the control of beneficially temperature and energy-conservation, mixed material carries out three bafflings or repeatedly in shell and tube reactor
Baffling back-mixing.
(3) during the mixture system in step (2) enters described advection regulator, hydrochloric acid, bran in described mixture system
Alcohol and thiourea continue to react and obtain furfuryl group isothiourea；When the liquid level in advection regulator reaches setting position, by overflowing
Streamed discharging, then reacts generation furfurylmercaptan with sodium hydrate aqueous solution, and the pH of reaction system remains about 8.
Embodiment 4
A kind of method of system continuous synthesis furfurylmercaptan used in embodiment 2, comprises the following steps:
1, prepare raw material: mass concentration is the hydrochloric acid solution of 30%, leave in hydrochloric acid tank 9, furfuryl alcohol (content >
99%), leave in furfuryl alcohol storage tank 6, in the molten storage tank of thiourea system 7 thiourea in mass ratio: water=42:100 is configured to saturated thiourea
Aqueous solution, the sodium hydroxide solution that thiourea solution storage tank 8 is left in transfer in, mass concentration is 20% exists water-soluble at sodium hydroxide
In liquid storage tank 5.
2, furfurylmercaptan continuous production processes:
(1) opening hydrochloric acid dosing pump, pressure shows normally, gradually opens hydrochloric acid inlet valve, is transferred to 0.5M3/ h pumps into salt
Acid.
(2), after stability of flow, it is passed through steam heating shell and tube reactor 3 to 55 DEG C ± 1 by steam inlet 3-1 simultaneously
DEG C, bottom stable charging to advection insulation reaction device 4.
(3) open thiourea and furfuryl alcohol dosing pump simultaneously, gradually open thiourea inlet valve, flow is transferred to 0.5M3/h.Then
Open furfuryl alcohol inlet valve, flow is adjusted to 0.23M3/ h stably feeds.
Now in shell and tube reactor 3, part hydrochloric acid, furfuryl alcohol and thiourea react and generate furfuryl group isothiourea.
During steam heating, steam is entered by steam inlet, owing to the reaction of hydrochloric acid, furfuryl alcohol and thiourea generates furfuryl group isothiourea
For exothermic reaction, so when temperature is higher than 56 DEG C, needing cooling to reach suitable reaction temperature, now, by cooling
Water water inlet 3-2 is passed through cooling water.Steam heating and cooling water cooling with the use of so that temperature is maintained at 54～56 DEG C.
Reach to react temperature required fully to be reacted and to save for better controling over hydrochloric acid, furfuryl alcohol and thiourea further
Energy consumption, mixed material carries out three bafflings or repeatedly baffling back-mixing in shell and tube reactor.
(4) the furfurylmercaptan changes of contents in advection insulation reaction device 4 of detection in every 10 minutes, simultaneously according to content situation
Suitably adjust the effect that furfuryl alcohol inlet amount reaches to react completely.
(5) measure advection insulation reaction device 4 bottom discharge outlet reacted hydrochloric acid residual concentration, the most suitably increase
Add and reduce the inlet amount of hydrochloric acid and reach suitable.
(6) when the liquid level during advection stablizes reactor 4 reaches the discharging opening of bottom, by overflowing that discharging opening 4-1 connects
Go out discharge nozzle and enter the pipeline leading to steam distillation device 10, open sodium hydroxide solution pump, pump into sodium hydroxide water-soluble simultaneously
Liquid and furfuryl group isothiourea react generation furfurylmercaptan, and to be neutralized to pH in pipeline be about 8, enter in steam distillation device 10.
(7) when liquid level reaches at 1/3 in steam distillation device 10, opening steam distillation, temperature controls at 90～98 DEG C,
Entering the second quantizer 13 after the condensation of steam condensed device 12, after distillate layering, upper oil phase enters crude product storage tank 14, aqueous phase
It is back to prepare hydrochloric acid and thiourea solution.
(8) steam distillation device bottom water liquid is by liquid level board 1/3～2/3 position in Valve controlling tank, and the end goes out liquid (does not has warp
Overflash, material out bottom steam distillation device) separate oil phase through first layer device 11 and enter crude product storage tank 14, aqueous phase
Content according to the furfurylmercaptan in aqueous phase and raw material components determines whether that adding reactor again continues reaction or deallocation salt manufacturing acid solution.
After keeping system balancing, aqueous phase drains into treatment center of sewage and processes.Now, crude product storage tank 14 is furfurylmercaptan crude product,
Productivity is more than 85%.
(9) it addition, carry out to preferably contribute to reaction positive direction, first material mixes at venturi mixer 2
Close, when material is by venturi mixer 2, produces negative pressure and the partial material in advection insulation reaction device 4 is sucked, participate in anti-
Should, by Valve controlling suction volume.
Further, obtaining finished product furfurylmercaptan after the crude product in crude product storage tank 14 is refined after reaching some, its purity can
Reach more than 99%.
Above-described embodiment is the present invention preferably embodiment, but embodiments of the present invention are not by above-described embodiment
Limit, the change made under other any spirit without departing from the present invention and principle, modify, substitute, combine, simplify,
All should be the substitute mode of equivalence, within being included in protection scope of the present invention.
Claims (10)
1. a continuous reaction apparatus, is characterized in that: include mixed flow reactor and advection insulation reaction device；Wherein,
Described mixed flow reactor include shell and tube reactor, venturi mixer and be connected bottom described shell and tube reactor
Low head；Several vertical ducts for material reaction are included, between described vertical duct inside described shell and tube reactor
And/or tool accommodates steam and/or the gap of cooling water between described vertical duct and described tubular reaction wall；Described tubulation
At least provided with steam inlet, cooling water intake and condensation-water drain on formula reactor wall；Described venturi mixer passes through institute
State low head to be connected with the vertical duct in described shell and tube reactor；
Described advection insulation reaction wall is provided with several material outlets, and described advection insulation reaction device is internal with described
Vertical duct in shell and tube reactor is connected.
2. device as claimed in claim 1, is characterized in that: be provided with in described low head and can seal described shell and tube reactor
The lower baffling cap of vertical duct of peripheral annular portion, in the bottom of described advection insulation reaction device or shell and tube reactor
The upper baffling cap of the vertical duct that can seal the remainder removing described peripheral annular portion it is provided with in top；Preferably,
Described lower baffling cap is a ring-type end enclosure structure or ring-like end enclosure structure, and upper baffling cap is an end enclosure structure, described upper folding
Stream cap and lower baffling cap cooperate the material baffling that realizes in mixed flow reactor three times.
3. device as claimed in claim 1, is characterized in that: described mixed flow reactor and advection insulation reaction device are for being arranged above and below
Or be left-right situs.
4. device as claimed in claim 1, is characterized in that: be additionally provided with emptying evacuation port on described tubular reaction wall；Excellent
Choosing, described venturi mixer is also connected with inside advection insulation reaction device.
5. device as claimed in claim 1, is characterized in that: described advection insulation reaction device is sequentially provided with three from top to bottom and goes out
Material mouth；Preferably, described three discharging openings are separately positioned on advection and stablize the position, upper, middle and lower of wall；Preferably, described company
Continuous reaction unit is provided with several densitometers, pH meter and thermometer；Preferably, the draw ratio of described vertical duct be 45～
55:1, it is further preferred that the draw ratio of described vertical duct is 50:1.
6. successive reaction produces a process system for furfurylmercaptan, it is characterized in that: at least include any one of Claims 1 to 5
Described continuous reaction apparatus, several material pots, sodium hydrate aqueous solution storage tank, steam distillation device, condenser, first point
Layer device and the second quantizer；
Described material pot connects the venturi mixer in described continuous reaction apparatus；
The discharging opening of the advection insulation reaction device in described continuous reaction apparatus is connected by described sodium hydrate aqueous solution storage tank
The inlet of described steam distillation device, the liquid outlet of described steam distillation device is connected with the inlet of first layer device；
The distillate outlet of described steam distillation device is connected by the inlet of condenser with described second quantizer.
7. process system as claimed in claim 6, is characterized in that: described successive reaction production system also includes crude product storage tank,
Described first layer device and the second quantizer are also connected with crude product storage tank, make the oil phase in first layer device and the second quantizer
Enter in crude product storage tank.
8. use the method that the continuous reaction apparatus according to any one of Claims 1 to 5 synthesizes furfurylmercaptan, its feature
It is to comprise the following steps:
(1) raw material is prepared: hydrochloric acid solution, furfuryl alcohol, thiourea solution and sodium hydrate aqueous solution；
(2) hydrochloric acid solution, furfuryl alcohol and thiourea solution are entered the vertical duct in described mixed flow reactor according to the ratio of setting
In, heated by steam and/or cool down the cooling effect of water and make hydrochloric acid, furfuryl alcohol and thiourea reach to react temperature required, and
Part hydrochloric acid, furfuryl alcohol and thiourea react and generate furfuryl group isothiourea；
(3) mixture system in step (2) enters in described advection regulator, hydrochloric acid in described mixture system, furfuryl alcohol and
Thiourea continues to react and obtains furfuryl group isothiourea；Overflow type is passed through when the liquid level in advection regulator reaches setting position
Discharging, then reacts generation furfurylmercaptan with sodium hydrate aqueous solution.
9. the method described in claim 8, is characterized in that: in step (1), and the mass concentration of described hydrochloric acid is 25～35%, excellent
Choosing, the mass concentration of described hydrochloric acid is 30%；The purity of described furfuryl alcohol is 99%；Described thiourea solution be thiourea and water by
Saturated thiourea solution according to mass ratio 42:100 mixed configuration；The mass concentration of described sodium hydrate aqueous solution is 15
～25%, it is preferred that the mass concentration of described sodium hydrate aqueous solution is 20%；
In step (2), temperature required is 50～60 DEG C, it is preferred that described temperature is 54～56 DEG C；
In step (2), the flow proportional that described hydrochloric acid solution, furfuryl alcohol and thiourea solution enter in described flow mixing device is 0.5:
0.5:(0.2～0.5)；
In step (2), described mixed material carries out three bafflings or repeatedly baffling back-mixing in shell and tube reactor；
In step (3), after adding sodium hydroxide so that the pH of the mixture system in advection insulation reaction device is 7.5～8.5,
Preferably pH is 8.
10. method as claimed in claim 8, is characterized in that: after step (3) generates furfurylmercaptan, product furfurylmercaptan enters
Enter in steam distillation device, enter the second quantizer after distillate condensation, isolate the first oil phase and the first aqueous phase, the first oil phase
Enter in furfurylmercaptan crude product tank；
Liquid level in described steam distillation device need to be maintained at setting position, and the end goes out liquid and isolates the second oil phase through first layer device
With the second aqueous phase, the second oil phase enters furfurylmercaptan crude product tank.
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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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