Method and device for treating waste liquid containing water-soluble alcohol, zinc chloride and zinc powder
Technical Field
The invention relates to a method and a device for treating waste liquid containing water-soluble alcohol, zinc chloride and zinc powder, belonging to the technical field of a preparation method of hexafluoro-1, 3-butadiene.
Background
Hexafluoro-1, 3-butadiene, also known as perfluorobutadiene, HFBD for short, of formula C4F6. Hexafluoro-1, 3-butadiene is an important monomer for synthetic resins and fluorine-containing substances. At present, the application of hexafluoro-1, 3-butadiene is mainly focused on the plasma medium etching processing technology of semiconductor products. With conventional plasma etching gas CF4、C2F6、C3F8And NF3Compared with C4F6Has faster etching speed, high etching selectivity and high aspect ratio. In addition, according to international convention requirements such as the kyoto protocol and the paris agreement and requirements of international low-carbon social construction, the electronic gas using the low-temperature chamber effect needs to be developed, and the Global Warming Potential (GWP) value of hexafluoro-1, 3-butadiene is only 290, the atmospheric lifetime is only 1.9d, and the electronic gas is a very green choice.
In recent years, various studies have been made on the synthesis of hexafluoro-1, 3-butadiene, among which the preparation of hexafluoro-1, 3-butadiene by reacting tetrachlorohexafluorobutane with zinc powder is a more common method. The reaction is promoted by using water-soluble alcohol as a solvent, and after the reaction is finished, organic waste liquid consisting of the water-soluble alcohol, zinc chloride and zinc powder is not easy to treat, and particularly, the waste liquid contains more zinc powder and soluble salts; at present, the waste liquid is generally treated by adopting a traditional distillation process, but the process is difficult to effectively separate the waste liquid containing water, water-soluble alcohol, zinc chloride and zinc powder from soluble salt, and the waste liquid treated by the distillation process can cause the problems of environmental pollution and the like if being directly discharged.
Therefore, it is an urgent need to solve the problems of the art to develop a method and apparatus for effectively separating the waste liquid containing water, water-soluble alcohol, zinc chloride and zinc powder from soluble salts, and the waste liquid after treatment will not cause environmental pollution.
Disclosure of Invention
In view of the above, the present invention is directed to a method and an apparatus for treating a waste liquid containing water-soluble alcohol, zinc chloride and zinc powder, which are used to effectively separate and treat the waste liquid containing water, water-soluble alcohol, zinc chloride and zinc powder from soluble salts, and the treated waste liquid does not cause environmental pollution.
In order to achieve the purpose of the invention, the following technical scheme is provided.
A treatment method of waste liquid containing water-soluble alcohol, zinc chloride and zinc powder comprises the following steps:
adding waste liquid containing water-soluble alcohol, zinc chloride and zinc powder into a settling tank for settling; after the sedimentation is finished, pressing the supernatant into a suction filtration tank, and transferring the lower-layer solid into a reaction kettle; vacuumizing and filtering the supernatant in the suction filtration tank, storing the filtrate in a filtrate storage tank, and transferring the filter residue into a reaction kettle;
replacing the reaction kettle with nitrogen in advance; adding a hydrochloric acid solution into the reaction kettle, adjusting the pH value to be 3-4, and adjusting the stirring speed to be 10-30 Hz; keeping nitrogen continuously purging in the reaction process to obtain reaction liquid;
and thirdly, after the reaction is finished, transferring the reaction liquid obtained in the second step to a film evaporator for evaporation, transferring the steam to a condenser for condensation, then, transferring the steam to a condensate storage tank for storage, and transferring the solid to drying equipment for drying to obtain the zinc chloride solid.
The method comprises the following steps:
preferably, the settling time is more than or equal to 24 hours, and the pressure of the vacuum filtration of the suction filtration tank is-0.08 MPa to-0.09 MPa.
In the preferable step (i), the filtrate in the filtrate storage tank is transferred to a condensate storage tank.
Step two:
preferably, the mass fraction of the hydrochloric acid solution is 2-10%.
Preferably, the reaction kettle is replaced by nitrogen in advance until the detected oxygen content is less than or equal to 100 ppm.
Step three:
preferably, the thin film evaporator is a wiped film evaporator.
Preferably, the liquid temperature of the reaction liquid before entering the wiped film evaporator is more than or equal to 60 ℃, and the evaporation pressure of the wiped film evaporator is-0.095 MPa to-0.099 MPa.
Preferably, the temperature of the refrigerant of the condenser is 3-7 ℃, the pressure of the drying equipment is-0.08 MPa-0.09 MPa, and the temperature is 100-150 ℃; preferably, the drying apparatus is a drying oven.
Preferably, quantitatively transferring the condensate of the condensate storage tank to the reaction kettle; the addition amount of the condensate is 0.5-2 times of the volume of the waste liquid.
The device is used in a method for treating the waste liquid containing the water-soluble alcohol, the zinc chloride and the zinc powder, and comprises a settling tank, a suction filtration tank, a reaction kettle, an evaporator, a condenser, a condensate storage tank, drying equipment and a filtrate storage tank.
The top of the settling tank is provided with a waste liquid inlet used for controlling the addition of waste liquid containing water-soluble alcohol, zinc chloride and zinc powder for settling; the top of the sedimentation tank is also provided with a supernatant outlet and is connected with a supernatant inlet of the suction filtration tank through a pipeline, and the supernatant is pressed into the suction filtration tank after the sedimentation is finished; the bottom of the settling tank is provided with a lower-layer solid outlet which is connected with a waste inlet of the reaction kettle through a pipeline and used for transferring the lower-layer solid obtained after settling into the reaction kettle.
The suction filtration tank is provided with a filtrate outlet and is connected with an inlet of the filtrate storage tank through a pipeline, and the filtrate outlet is used for storing filtrate obtained by vacuumizing and filtering supernatant in the suction filtration tank into a filtrate storage tank; a filter residue outlet is arranged at the bottom of the suction filtration tank and is connected with a waste material inlet of the reaction kettle through a pipeline, and filter residue obtained by vacuumizing and filtering supernatant in the suction filtration tank is transferred into the reaction kettle; preferably, the filtrate storage tank is provided with an outlet which is connected with the condensate storage tank through a pipeline and used for introducing the filtrate into the condensate storage tank.
A waste inlet is formed in the top of the reaction kettle and is used for introducing lower-layer solid and filter residue obtained after sedimentation; the top of the reaction kettle is also provided with a hydrochloric acid inlet for adding a hydrochloric acid solution for reaction; the top of the reaction kettle is also provided with a nitrogen inlet for introducing nitrogen for replacement, and the nitrogen is kept continuously purging in the reaction process; the top of the reaction kettle is also provided with a reaction kettle vent valve; the bottom of the reaction kettle is provided with a reaction liquid outlet and is connected with the inlet of the film evaporator through a pipeline for evaporating the reaction liquid.
A steam outlet of the thin film evaporator is connected with a steam inlet of the condenser through a pipeline and is used for condensing steam into condensate; and an evaporation solid outlet of the thin film evaporator is connected with an inlet of the drying equipment through a pipeline and is used for transferring the evaporation solid to the drying equipment for drying to obtain a zinc chloride solid.
The outlet of the condenser is connected with the inlet of the condensate storage tank through a pipeline and is used for introducing condensate formed by condensing steam into the condensate storage tank for storage. Preferably, the condensate storage tank is provided with an outlet which is connected with the reaction kettle through a pipeline and used for transferring the condensate into the reaction kettle; the transfer amount of the condensate is 0.5-2 times of the volume of the waste liquid.
Valves are provided at the inlet and outlet for on-off control, as required.
Advantageous effects
1. The invention provides a method and a device for treating waste liquid containing water-soluble alcohol, zinc chloride and zinc powder, wherein the waste liquid containing the water-soluble alcohol, the zinc chloride and the zinc powder is pretreated, then the waste liquid is reacted with a hydrochloric acid solution, so that the zinc powder is converted into a zinc chloride aqueous solution, original zinc chloride in the waste liquid and zinc chloride produced in a reaction kettle are completely evaporated by a film evaporator to obtain a zinc chloride solid, and finally the waste liquid containing the water, the water-soluble alcohol, the zinc chloride and the zinc powder and soluble salt can be effectively separated, no harmful substance is discharged in the process, and the treated condensate liquid can not cause environmental pollution.
2. The invention provides a method and a device for treating waste liquid containing water-soluble alcohol, zinc chloride and zinc powder. The recovered solvent is recycled, so that the production cost is greatly saved.
3. The invention provides a method and a device for treating waste liquid containing water-soluble alcohol, zinc chloride and zinc powder, wherein the purity of zinc chloride solid obtained by evaporation of a thin film evaporator is up to more than 93 percent, and the zinc chloride solid can be recycled as a byproduct to generate economic benefit.
Drawings
Fig. 1 is a schematic structural diagram of a device for treating waste liquid containing water-soluble alcohol, zinc chloride and zinc powder in example 1.
Wherein, 1-settling tank, 2-suction filtration tank, 3-reaction kettle, 4-evaporator, 5-condenser, 6-condensate storage tank, 7-drying equipment, 8-filtrate storage tank
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention relates to a treatment device for waste liquid containing water-soluble alcohol, zinc chloride and zinc powder, which has the main design idea that: hydrochloric acid and waste liquid react in a reaction kettle 3 to convert zinc powder into a zinc chloride aqueous solution, and original zinc chloride in the reaction waste liquid and zinc chloride produced in the reaction kettle 3 are completely evaporated by a wiped film evaporator 4 to obtain a zinc chloride solid.
Through the arrangement of the overall design idea, zinc powder, soluble salt and the like in the waste liquid can be effectively separated, and the waste liquid after treatment can not cause environmental pollution.
Example 1
A treatment device for waste liquid containing water-soluble alcohol, zinc chloride and zinc powder is shown in figure 1 and comprises a settling tank 1, a suction filtration tank 2, a reaction kettle 3, an evaporator 4, a condenser 5, a condensate storage tank 6, a drying device 7 and a filtrate storage tank 8.
The top of the settling tank 1 is provided with a waste liquid inlet used for controlling the addition of waste liquid containing water-soluble alcohol, zinc chloride and zinc powder, settling and separating solid matters and liquid matters in the waste liquid; the top of the sedimentation tank 1 is also provided with a supernatant outlet and is connected with a supernatant inlet of the suction filtration tank 2 through a pipeline, and after sedimentation is finished, the supernatant is pressed into the suction filtration tank 2 by a material transfer pump; the bottom of the settling tank 1 is provided with a lower-layer solid outlet which is connected with a waste inlet of the reaction kettle 3 through a pipeline and used for collecting lower-layer solids obtained after settling, wherein the lower-layer solids are mainly zinc powder and are transferred into the reaction kettle 3.
The suction filtration tank 2 is provided with a filtrate outlet and is connected with an inlet of a filtrate storage tank 8 through a pipeline, and the filtrate is used for storing filtrate obtained by vacuumizing and filtering supernatant in the suction filtration tank 2 into the filtrate storage tank 8, wherein the filtrate is mainly a mixed solution of a zinc chloride solution, water and water-soluble alcohol; a filter residue outlet is formed in the bottom of the suction filtration tank 2 and is connected with a waste material inlet of the reaction kettle 3 through a pipeline, supernatant in the suction filtration tank 2 is collected and subjected to vacuum filtration, and filter residues obtained are transferred into the reaction kettle 3, wherein the filter residues comprise part of zinc powder, so that the separation effect of waste liquid treatment is further improved; the filtrate storage tank 8 is provided with an outlet which is connected with the condensate storage tank 6 through a pipeline and is used for introducing the filtrate into the condensate storage tank 6.
A waste inlet is formed in the top of the reaction kettle 3 and is used for introducing lower-layer solids obtained after sedimentation is finished; the top of the reaction kettle 3 is also provided with a hydrochloric acid inlet for adding a hydrochloric acid solution to react with the lower-layer solid; the top of the reaction kettle 3 is also provided with a nitrogen inlet for introducing nitrogen for replacement, and the nitrogen is kept continuously purging in the reaction process; the top of the reaction kettle 3 is also provided with a reaction kettle vent valve; before feeding into the reaction kettle 3, nitrogen is used for replacement in advance, and then feeding is carried out for reaction, wherein the reaction mainly comprises the replacement reaction of zinc powder and hydrogen ions in hydrochloric acid solution, so that insoluble zinc powder is converted into soluble zinc ions and enters into reaction liquid. The bottom of the reaction kettle 3 is provided with a reaction liquid outlet and is connected with the inlet of the film evaporator 4 through a pipeline for evaporating the reaction liquid.
A steam outlet of the thin film evaporator 4 is connected with a steam inlet of the condenser 5 through a pipeline and is used for condensing steam into condensate, mainly water and water-soluble alcohol; and an evaporated solid outlet of the thin film evaporator 4 is connected with an inlet of the drying device 7 through a pipeline and is used for transferring the evaporated solid to the drying device 7 for drying to obtain a zinc chloride solid.
The outlet of the condenser 5 is connected with the inlet of the condensate storage tank 6 through a pipeline and is used for introducing condensate formed by condensing steam into the condensate storage tank 6 for storage. Preferably, the condensate storage tank 6 is provided with an outlet which is connected with the reaction kettle 3 through a pipeline and is used for transferring the condensate into the reaction kettle 3; the transfer amount of the condensate is 0.5-2 times of the volume of the waste liquid.
The thin film evaporator 4 is a wiped film evaporator 4.
The drying device 7 is a drying oven.
Valves are provided at the inlet and outlet for on-off control, as required.
Examples 2 to 4
A treatment method of waste liquid containing water-soluble alcohol, zinc chloride and zinc powder comprises the following steps:
(1) adding waste liquid containing water-soluble alcohol, zinc chloride and zinc powder into a settling tank 1 for settling; after the sedimentation is finished, pressing the supernatant into the suction filtration tank 2 by using a material transfer pump, collecting the lower-layer solid and transferring the lower-layer solid into the reaction kettle 3; vacuumizing and filtering the supernatant in the suction filtration tank 2, storing the filtrate in a filtrate storage tank, collecting filter residues and transferring the filter residues into a reaction kettle 3; the filtrate from the filtrate tank 8 is transferred to the condensate tank 6.
(2) The reaction kettle 3 is replaced by nitrogen in advance, and the oxygen content is detected to be lower than 100 ppm; adding a hydrochloric acid solution into a reaction kettle 3, wherein the addition amount of the hydrochloric acid solution is based on the adjustment of pH, and the addition is stopped when the pH is lower than 3, so that zinc powder in the waste liquid is fully reacted, the pH value is adjusted to be 3-4 as a reaction end point, and the stirring speed is adjusted to be 10-30 Hz, so as to obtain a reaction liquid; and the nitrogen is kept continuously purged in the reaction process, so that the hydrogen is prevented from accumulating.
(3) And (3) after the reaction is finished, transferring the reaction liquid obtained in the step (2) to a film evaporator 4 for evaporation, transferring the steam to a condenser 5 for condensation, then, transferring the steam to a condensate storage tank 6 for storage, and transferring the solid to a drying device 7 for drying to obtain a zinc chloride solid.
The specific raw material ratios and treatment conditions of examples 2 to 4 are shown in table 1 below:
TABLE 1
Through detection, the purity of the zinc chloride solid product obtained in the embodiment 2-4 respectively reaches 93%, 93.5% and 93.8%. Therefore, the method disclosed by the invention can effectively separate the zinc powder, the zinc chloride solution, the water and the water-soluble alcohol, and the obtained zinc chloride solid product has high purity, can be recycled as a byproduct, and has certain economic benefit.
In order to further improve the performance of the treatment method of the waste liquid containing water-soluble alcohol, zinc chloride and zinc powder, the filtrate in the filtrate storage tank 8 can be transferred to the condensate storage tank 6; transferring the condensate in the condensate storage tank 6 to the reaction kettle 3. Water and water-soluble alcohol in the waste liquid can be extracted out by vacuumizing and filtering the waste liquid, and the waste liquid can be continuously used as a solvent in the reaction kettle 3. The recovered solvent is recycled, so that the production cost is greatly saved. The addition amount of the condensate is 0.5-2 times of the volume of the waste liquid.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.