CN209854033U - Continuous production device of dithiocyano-methane - Google Patents
Continuous production device of dithiocyano-methane Download PDFInfo
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- CN209854033U CN209854033U CN201822139468.5U CN201822139468U CN209854033U CN 209854033 U CN209854033 U CN 209854033U CN 201822139468 U CN201822139468 U CN 201822139468U CN 209854033 U CN209854033 U CN 209854033U
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Abstract
The utility model discloses a continuous production device of dithiocyano-methane. The continuous production device of the dithiocyano-methane is formed by sequentially and circularly connecting a continuous tubular reactor provided with internal components, a crystallization device, a solid-liquid separation device and a desalting device, wherein the solid-liquid separation device is also connected with a drying device. The utility model discloses a dithiocyano methane continuous production device has serialization production, stable control reaction condition, improves the characteristics of product yield.
Description
Technical Field
The utility model relates to a continuous production device of dithiocyano-methane.
Background
Dithiocyanomethane (MBT), also known as methylene dithiocyanate, has CAS number 6317-18-6 and has the chemical structure:the dithiocyano-methane is a high-efficiency broad-spectrum bactericide with excellent performance and has stronger killing capability on bacteria, mould and algae. When the dosage of the dithiocyano-methane is 10-100 mg/kg, the sterilization rate is 99%, and the use effect is better when the pH value is 7. Has good killing and inhibiting effects on main bacteria, fungi and algae existing in industrial water and protozoa, and is especially effective on sulfate reducing bacteria. Dithiocyanomethanes are non-oxidizing biocides that do not suffer a decrease in activity due to contaminants, debris or other particulates in the aqueous system. Meanwhile, the toxicity is reduced after hydrolysis, which is beneficial to discharge. Therefore, the dithiocyano-methane is widely used as a sterilization, algae removal and slime prevention agent for industrial circulating cooling water, sewage waste water and oilfield flooding, and can also be used in paper-making and food packaging paper-board industries.
The dithiocyano-methane can be prepared by respectively reacting thiocyanate (sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate and the like) with alkyl halide (dichloromethane, bromochloromethane, dibromomethane, diiodomethane and the like) under different conditions and auxiliary agents. At present, a kettle type reaction is generally adopted, thiocyanate and alkyl halide are respectively added into a reaction kettle, and crystallization is carried out after the reaction is finished. In the reaction, water is generally used as a solvent, and a phase transfer catalyst needs to be added or the reaction is carried out at high temperature and high pressure because the compatibility of the alkyl halide and the water is poor. The synthetic reaction of dithiocyano-methane is carried out at an oil-water two-phase interface, the mixing intensity of a kettle type reactor is low, the accurate control of the reaction degree cannot be realized, and even if the reaction is carried out at high temperature and high pressure for a long time, thiocyanate and alkyl halide cannot completely react, so that the product yield is low, the number of byproducts in a crude product is large, and a qualified product can be obtained only by carrying out complicated refining steps. Therefore, the development of an efficient continuous production method, the control of the reaction degree, the reduction of byproducts and the improvement of the product yield is the best way for realizing the clean production of MBT.
CN103387526A adopts ammonium thiocyanate and dichloromethane to produce MBT through the process steps of synthesis, crystallization, product filtration, product washing, product secondary filtration, product refining, drying and the like, the synthesis time is more than 6 hours, the product yield reaches 80 percent, but the amount of generated waste water is extremely large and exceeds 6 times of the product weight, and the steps are complicated. The research on the preparation process of dithiocyano-methane (Wangchun, et al, fine and special chemicals, 2011,19 (7): 29-31) researches on the synthesis of dithiocyano-methane by using dibromomethane and sodium thiocyanate as raw materials, ethanol-water as a solvent and tetrabutylammonium bromide as a phase transfer catalyst, wherein the reaction time is 5 hours, and the reaction yield is 74%. Because the price of dibromomethane is relatively high, the problem of recycling bromine in byproducts must be considered in production, and some problems exist in cost and process. After the research on the dithiocyano-methane circulation process (towering and the like, fine and special chemicals, 2017,25(2):36-39) is used for recycling sodium thiocyanate, the product yield only reaches about 76%, and an alcohol solvent is used during synthesis, so that the cost and the environmental protection pressure are increased.
The existing MBT production method still has the defects that the reaction degree cannot be accurately controlled, a kettle type reactor is adopted more, the number of byproducts is large, the yield is low, the productivity is too low and the like, and the clean continuous production of the MBT is difficult to realize. Therefore, a set of MBT continuous production apparatus is urgently needed to be developed, which can realize clean continuous production while reducing environmental protection pressure.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a dithiocyano methane's continuous production device, this kind of device can realize strengthening reaction, accurate control reaction condition and improve the effect of result yield.
The utility model adopts the technical proposal that:
a continuous production device of dithiocyano-methane is composed of a continuous tubular reactor with internal components, a crystallizing device, a solid-liquid separating device and a desalting device which are sequentially connected in a circulating manner, wherein the solid-liquid separating device is also connected with a drying device.
Preferably, in the continuous dithiocyano-methane production device, the continuous reactor provided with the internal components comprises a reaction tube, an internal component, an external jacket, a feeding tube and a connecting flange.
Preferably, the continuous tubular reactor provided with the inner component is provided with a reaction tube, the inner component is arranged in the reaction tube, the outer jacket of the reaction tube is arranged outside the reaction tube, the feeding tube is vertically arranged in the reaction tube, and two ends of the reaction tube are provided with connecting flanges.
Preferably, in the continuous tubular reactor provided with the internals, the feed pipes are vertically arranged at one third and two thirds of the length of the reaction tube, respectively.
Preferably, in the continuous tubular reactor provided with the internal member, the outlet of the feeding pipe is arranged on the central shaft of the reaction pipe; preferably, the inlet of the feeding pipe is also connected with a feeding pump.
Preferably, in the continuous tubular reactor provided with the internals, the internals are arranged vertically or crosswise in the reaction tubes.
Preferably, in the continuous tubular reactor provided with the internals, the internals comprise one or more of straight plates, corrugated plates and twisted blades.
Preferably, in the continuous tubular reactor provided with internals, the reaction tubes are made of a metal resistant to pressure, temperature and corrosion.
Preferably, in the continuous production device of the dithiocyano-methane, the solid-liquid separation device is one or more of a filter pressing device, a suction filtration device and a centrifugal separation device.
Preferably, in the continuous production device of the dithiocyano-methane, the desalting device is one or more of an electric desalting device, a concentration desalting device, a reverse osmosis desalting device, a filtration desalting device, a gel desalting device and an ion exchange desalting device; further preferably, the electric desalting device can be an electrodialysis device, an electric adsorption device or an electric deionization desalting device; the concentration desalination can be a distillation desalination device; the filtering desalination device can be a nanofiltration desalination device or an ultrafiltration desalination device.
The utility model has the advantages that:
the utility model discloses a dithiocyano methane continuous production device has serialization production, stable control reaction condition, improves the characteristics of product yield.
The utility model adopts a continuous reactor. Compared with a kettle type reactor, the continuous reactor has the advantages of improving mixing intensity, shortening reaction time, accurately controlling reaction degree and improving product yield, and can greatly improve the space-time efficiency of the reactor and reduce the cost.
The device of the utility model is used for producing the dithiocyano-methane, and the reaction effect is improved by strengthening the mixing strength of the reaction materials in the reaction tube; cooling or heating medium is introduced into the jacket, and the reaction condition is accurately controlled; adding materials in the middle of the reaction tube, and controlling the reaction concentration of the materials to ensure that the materials reach the optimal reaction concentration. Finally, the effects of continuous production, stable control of reaction conditions and improvement of product yield are achieved.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention;
FIG. 2 is a schematic view of a continuous tube reactor with internals.
Detailed Description
Fig. 1 is a schematic diagram of the device of the present invention. In FIG. 1, 1-continuous tubular reactor equipped with internals, 2-crystallization apparatus, 3-solid-liquid separation apparatus, 4-desalting apparatus, and 5-drying apparatus. The continuous production apparatus for dithiocyanomethane of the present invention is further described with reference to FIG. 1. The utility model discloses a dithiocyano methane continuous production device is by continuous tubular reactor 1, crystallization device 2, solid-liquid separation equipment 3, the desalination device 4 that sets up the inner member in proper order the circulation connection constitute, and solid-liquid separation equipment 3 still is connected with drying device 5.
Furthermore, a wet product (solid product) outlet of the solid-liquid separation device is connected with the dryer, and a mother liquid (liquid product) outlet of the solid-liquid separation device is connected with the desalting device. Drying the wet product to obtain the dithiocyano-methane product. And a desalting mother liquor outlet obtained by the desalting device is connected with an inlet of the continuous tubular reactor provided with the internal member, and the obtained desalting mother liquor is recycled. The byproduct salt and a small amount of waste water obtained by the desalting device can be subjected to environmental protection treatment.
The solid-liquid separation device can be selected from one or more of a filter pressing device, a suction filtration device and a centrifugal separation device. The desalting device can be selected from one or more of electric desalting device, concentration desalting device, reverse osmosis desalting device, filtration desalting device, gel desalting device and ion exchange desalting device.
FIG. 2 is a schematic view of a continuous tube reactor with internals. In FIG. 2, 1-reaction tube, 2-tube internal member, 3-tube external jacket, 4-connecting flange, 5-feeding tube. The continuous tube reactor provided with internals is further illustrated below with reference to FIG. 2. The continuous reactor provided with the internals comprises a reaction tube 1, an inner pipe 2, an outer pipe jacket 3, a feeding tube 5 and a connecting flange 4.
Furthermore, a reaction tube 1 is arranged in the continuous tubular reactor provided with the inner component, the inner component 2 is arranged in the reaction tube 1, an outer jacket 3 is arranged outside the reaction tube 1, and two ends of the reaction tube 1 are provided with connecting flanges 4. A feed pipe 5 is vertically arranged at one third and two thirds of the length position of the reaction pipe 1 respectively, the outlet position of the feed pipe 5 is arranged on the central shaft of the reaction pipe 1, and the inlet of the feed pipe 5 is also connected with a feed pump. The reaction tube 1 is provided with an inner tube member 2 vertically or crosswise. The pipe inner member 2 is composed of one or more of straight plates, corrugated plates and twisted blades. By installing the pipe internal member, the fluid can simultaneously realize the effects of laminar flow and turbulent flow in the reaction pipe. The reaction tube 1 is made of a metal resistant to pressure, temperature and corrosion. The external pipe jacket 3 can be used for introducing heating medium (steam or hot water) or cooling medium (circulating water or chilled water). The connecting flange is used for being connected with other devices, and a complete production flow is realized.
The connection of the utility model is through the connection of pipeline and/pipeline etc., belongs to the conventional technology in this field. The present invention will be described in further detail with reference to specific examples. The starting materials or the apparatuses used in the examples were obtained from conventional commercial sources unless otherwise specified.
Example 1
Example 1 a dithiocyanomethane continuous production apparatus, which was composed of a continuous tubular reactor with internals, a crystallization apparatus, a centrifugal separation apparatus, and a concentration and desalination apparatus, which were connected in sequence, and the centrifugal separation apparatus was also connected to a drying apparatus. Wherein, be equipped with a reaction tube in the continuous tubular reactor who sets up the internals, the corrugated plate internals is installed to the cross in the reaction tube, makes the abundant high strength of material mix. The outside of the reaction tube is provided with a tube jacket, and low-pressure steam is introduced into the tube jacket. The one third and the two thirds of the length of the reaction tube are respectively and vertically provided with a feed tube, the outlet of the feed tube is arranged on the central shaft of the reaction tube, and the inlet of the feed tube is also connected with a feed pump. And two ends of the reaction tube are provided with connecting flanges.
Dithiocyanomethane was continuously produced using the apparatus of example 1. Adding desalting mother liquor and dichloromethane into a continuous tubular reactor provided with an inner component, adding ammonium thiocyanate saturated solution from a middle feeding pipe of the reactor, wherein the concentration of ammonium thiocyanate in the desalting mother liquor is 300g/L, the reaction molar ratio of ammonium thiocyanate to dichloromethane is 4:1, the reaction temperature is 95 ℃, the reaction pressure (gauge pressure, the same below) is 0.6MPa, and the retention time in the reactor is 30 min. Introducing the dithiocyano-methane reaction liquid obtained by the continuous tubular reactor into a crystallizing device for cooling crystallization, and cooling to 25 ℃ for crystallization for 2 h. Then, solid-liquid separation is performed by a centrifugal separation device, and the obtained wet product (solid product) is washed with a small amount of water and then enters a drying device for vacuum drying. The drying temperature is 50 deg.C, the vacuum degree is 0.08MPa, and the drying time is 2 h. Drying to obtain the dithiocyano-methane product. Desalting the mother liquor after solid-liquid separation by using a concentration desalting device to obtain desalted mother liquor, wherein the concentration of ammonium thiocyanate in the desalted mother liquor is 300g/L, and the concentration of ammonium chloride is 100 g/L. The desalting mother liquor returns to the continuous tubular reactor provided with the internals for circular reaction. The byproduct salt obtained by the desalting device is discharged for environment-friendly treatment, and simultaneously a small amount of wastewater is brought out, and the part of water is simply treated and then recycled for dissolving thiocyanate. It is noted that the mother liquor desalting does not need to remove all the salt, but only needs to remove part of the salt (the amount to be removed is subject to the condition that the salt is not saturated and separated out during solid-liquid separation after circulation), and the applicant's experiments show that the reaction can be promoted by the existence of the byproduct salt.
The yield of dithiocyanomethane as a product obtained by the apparatus of example 1 was 90.2%, and the product content was 96.5% by weight. The total amount of wastewater discharged in example 1 was 0.5t/t of product.
Example 2
Embodiment 2 dithiocyano methane continuous production device is by the continuous tubular reactor, crystallization device, suction filtration device, the electric desalination device circulation connection in proper order of setting up the internals and constitutes, and suction filtration device still is connected with drying device. The continuous tubular reactor provided with the internals was the same as the continuous tubular reactor of example 1 except that the straight internals were vertically installed in the reaction tube.
Dithiocyanomethane was continuously produced using the apparatus of example 2. Adding a desalting mother liquor and dichloromethane into a continuous tubular reactor provided with an inner member, adding a sodium thiocyanate saturated solution from a middle feeding pipe of the reactor, wherein the concentration of sodium thiocyanate in the desalting mother liquor is 400g/L, the reaction molar ratio of sodium thiocyanate to dichloromethane is 5:1, the reaction temperature is 100 ℃, the reaction pressure is 0.67MPa, and the retention time in the reactor is 50 min. Introducing the dithiocyano-methane reaction liquid obtained by the continuous tubular reactor into a crystallizing device for cooling crystallization, and cooling to 15 ℃ for crystallization for 2 h. Then solid-liquid separation is carried out through a suction filtration device, the obtained wet product (solid product) is washed by a small amount of water and enters a drying device for vacuum drying. The drying temperature is 60 deg.C, the vacuum degree is 0.07MPa, and the drying time is 2 h. Drying to obtain the dithiocyano-methane product. Desalting the mother liquor after solid-liquid separation by using an electric desalting device to obtain desalted mother liquor, wherein the concentration of sodium thiocyanate in the desalted mother liquor is 400g/L, and the concentration of sodium chloride is 150 g/L. The desalting mother liquor returns to the continuous tubular reactor provided with the internals for circular reaction. The byproduct salt obtained by the desalting device is discharged for environment-friendly treatment, and simultaneously a small amount of wastewater is brought out, and the part of water is simply treated and then recycled for dissolving thiocyanate.
The yield of dithiocyanomethane as a product obtained by the apparatus of example 2 was 93.4%, and the product content was 96.7% by weight. The total amount of wastewater discharged in example 2 was 0.8t/t of product.
Example 3
Embodiment 3 dithiocyano-methane continuous production device is by the continuous tubular reactor of setting up the internals, crystallization device, filter pressing device, concentrated desalination device circulation connection in proper order constitutes, and the filter pressing device still is connected with drying device. The continuous tubular reactor provided with the internals was the same as that of example 1 except that twisted blade internals were installed in a cross manner in the reaction tube and hot water was introduced into the jacket outside the tube.
Dithiocyanomethane was continuously produced using the apparatus of example 3. Adding the desalting mother liquor and dibromomethane into a continuous tubular reactor provided with an inner component, adding a sodium thiocyanate saturated solution from a middle feeding pipe of the reactor, wherein the concentration of sodium thiocyanate in the desalting mother liquor is 450g/L, the reaction molar ratio of sodium thiocyanate to dibromomethane is 6:1, the reaction temperature is 50 ℃, the reaction pressure is 0.05MPa, and the retention time in the reactor is 90 min. Introducing the dithiocyano-methane reaction liquid obtained by the continuous tubular reactor into a crystallizing device for cooling crystallization, and cooling to 25 ℃ for crystallization for 2 h. Then solid-liquid separation is carried out through a filter pressing device, the obtained wet product (solid product) is washed by a small amount of water and enters a drying device for vacuum drying. The drying temperature is 40 deg.C, the vacuum degree is 0.09MPa, and the drying time is 1 h. Drying to obtain the dithiocyano-methane product. Desalting the mother liquor after solid-liquid separation by using a concentration desalting device to obtain desalted mother liquor, wherein the concentration of sodium thiocyanate in the desalted mother liquor is 450g/L, and the concentration of sodium bromide in the desalted mother liquor is 150 g/L. The desalting mother liquor returns to the continuous tubular reactor provided with the internals for circular reaction. The byproduct salt obtained by the desalting device is discharged for environment-friendly treatment, and simultaneously a small amount of wastewater is brought out, and the part of water is simply treated and then recycled for dissolving thiocyanate.
The yield of dithiocyanomethane as a product obtained by the apparatus of example 3 was 91%, and the product content was 97.3% by weight. The total amount of wastewater discharged in example 3 was 0.6t/t of product.
Finally, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or replaced by other means without departing from the spirit and scope of the present invention, which should be construed as limited only by the appended claims.
Claims (9)
1. A continuous production device of dithiocyano-methane is characterized in that: the device is formed by sequentially and circularly connecting a continuous tubular reactor provided with internal components, a crystallization device, a solid-liquid separation device and a desalting device, wherein the solid-liquid separation device is also connected with a drying device.
2. The continuous dithiocyano-methane producing apparatus according to claim 1, wherein: the continuous reactor with the inner component comprises a reaction tube, an inner component, an outer jacket, a feeding tube and a connecting flange.
3. The continuous dithiocyanomethane production apparatus according to claim 2, wherein: the continuous tubular reactor with the inner component is provided with a reaction tube, the inner component is arranged in the reaction tube, the outer jacket of the reaction tube is arranged outside the reaction tube, the feeding tube is vertically arranged in the reaction tube, and two ends of the reaction tube are provided with connecting flanges.
4. A continuous dithiocyanomethane producing apparatus according to claim 2 or 3, wherein: in the continuous tubular reactor provided with the internals, feed pipes are vertically arranged at one third and two thirds of the length of the reaction pipe respectively.
5. The continuous dithiocyano-methane producing apparatus according to claim 4, wherein: in the continuous tubular reactor provided with the inner member, the outlet of the feed pipe is arranged on the central shaft of the reaction pipe.
6. A continuous dithiocyanomethane producing apparatus according to claim 2 or 3, wherein: in the continuous tubular reactor provided with the internals, the internals are arranged vertically or crosswise in the reaction tubes.
7. The continuous dithiocyano-methane producing apparatus according to claim 6, wherein: in the continuous tubular reactor provided with the internals, the internals comprise one or more of straight plates, corrugated plates and twisted blades.
8. The continuous dithiocyano-methane producing apparatus according to claim 1, wherein: the solid-liquid separation device is one or more of a filter pressing device, a suction filtration device and a centrifugal separation device.
9. The continuous dithiocyano-methane producing apparatus according to claim 1, wherein: the desalting device is one or more of an electric desalting device, a concentration desalting device, a reverse osmosis desalting device, a filtration desalting device, a gel desalting device and an ion exchange desalting device.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114349673A (en) * | 2021-12-23 | 2022-04-15 | 广东省科学院化工研究所 | Preparation method of dithiocyano-methane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114349673A (en) * | 2021-12-23 | 2022-04-15 | 广东省科学院化工研究所 | Preparation method of dithiocyano-methane |
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