CN114684989B - Method for treating triglycidyl isocyanurate production waste liquid - Google Patents
Method for treating triglycidyl isocyanurate production waste liquid Download PDFInfo
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Abstract
The invention relates to the technical field of waste liquid treatment, in particular to a method for treating triglycidyl isocyanurate production waste liquid. The processing method provided by the invention comprises the following steps: sequentially carrying out first acidolysis and intermittent reduced pressure distillation on TGIC production wastewater, mixing the obtained light yellow oily substance containing industrial salt with anhydrous methanol, and carrying out crystallization to obtain a methanol solution of inorganic salt and a first oily high-boiling substance; sequentially carrying out second acidolysis and first distillation on the methanol waste liquid to obtain anhydrous methanol and a methanol solution of a second oily high-boiling-point substance; carrying out second distillation on the methanol solution of the first oily high-boiling-point substance and/or the methanol solution of the second oily high-boiling-point substance to obtain anhydrous methanol and an oily high-boiling-point substance; and mixing the oily high-boiling-point substance and alkali liquor for cyclization reaction to obtain the epichlorohydrin. The treatment method is suitable for treating high COD and high salinity wastewater, and can also realize the treatment of methanol wastewater.
Description
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a method for treating triglycidyl isocyanurate production waste liquid.
Background
Triglycidyl isocyanurate (TGIC), white crystal, is mainly used as curing agent for carboxyl-containing polyester and carboxyl acrylic resin powder coating, and can also be used for manufacturing electrical insulating material laminated plates, printed circuits, various tools, adhesives, plastic stabilizers and the like. Has excellent heat resistance, weather resistance, light resistance, corrosion resistance and mechanical performance.
The solvent in the traditional TGIC production process is water, and TGIC production wastewater with high COD and industrial waste salt content is obtained while TGIC crude product is prepared; the crude TGIC product needs to be further recrystallized by hot methanol solution to obtain refined TGIC product, and a large amount of methanol waste liquid is generated in the process. The COD content of the TGIC production wastewater can be up to 1.8 multiplied by 10 generally 5 ～2.0×10 5 mg/L, the COD content of the methanol waste liquid can be generally as high as 4 multiplied by 10 4 ～5×10 4 mg/L. Therefore, neither of the above two waste liquids can be discharged directly.
At present, the treatment of TGIC production wastewater is mainly coagulation sedimentation-chemical oxidation-active bright adsorption method, but the method can only treat wastewater with lower COD content (less than or equal to 10000 mg/L) and does not carry out related research on the treatment of methanol waste liquid.
Disclosure of Invention
The invention aims to provide a method for treating triglycidyl isocyanurate production waste liquid, which is suitable for treating high-COD and high-salinity wastewater and can also realize the treatment of methanol wastewater, and the treatment method is simple and has low cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for treating triglycidyl isocyanurate production waste liquid, which comprises TGIC production waste water and/or methanol waste liquid, and comprises the following steps:
sequentially carrying out first acidolysis and intermittent reduced pressure distillation on TGIC production wastewater to obtain condensed water and a light yellow oily substance containing industrial salt;
mixing the industrial salt-containing light yellow oily substance with anhydrous methanol, and crystallizing to obtain a methanol solution of inorganic salt and a first oily high-boiling substance;
sequentially carrying out second acidolysis and first distillation on the methanol waste liquid to obtain anhydrous methanol and a methanol solution of a second oily high-boiling-point substance;
carrying out second distillation on the methanol solution of the first oily high-boiling-point substance and/or the methanol solution of the second oily high-boiling-point substance to obtain anhydrous methanol and an oily high-boiling-point substance;
and mixing the oily high-boiling-point substance and alkali liquor to carry out cyclization reaction to obtain the epichlorohydrin.
Preferably, the acid solution adopted by the first acidolysis is a sulfuric acid solution with the mass concentration of 65-68%;
the initial pH of the first acidolysis is = 1-2, the temperature is 50-70 ℃, and the time is 1-2 h.
Preferably, the pressure of the batch type reduced pressure distillation is 40-45 kPa, the temperature is 75-85 ℃, and the time is 5-8 h.
Preferably, after the condensed water is obtained, the condensed water is mixed with a chlorine dioxide solution and then discharged;
the mass concentration of the chlorine dioxide solution is 1.0%.
Preferably, the volume ratio of the light yellow oil containing industrial salt to the anhydrous methanol is 1: (2-3).
Preferably, the acid solution used for the second acidolysis is a hydrochloric acid solution with the mass concentration of 30-35%;
the initial pH of the second acidolysis is = 2-3, the temperature is 40-50 ℃, and the time is 1-2 h.
Preferably, the temperature of the first distillation is 80-90 ℃ and the time is 1-3 h.
Preferably, the second distillation is an atmospheric distillation; the temperature of the second distillation is 80-90 ℃, and the time is 1-2 h.
Preferably, the alkali liquor comprises 35-45% of sodium hydroxide aqueous solution by mass concentration;
the volume ratio of the oily high-boiling residue to the alkali liquor is 1: (1.2-1.5).
Preferably, the temperature of the cyclization reaction is 75 ℃ and the time is 1.5min.
The invention provides a method for treating triglycidyl isocyanurate production waste liquid, wherein the triglycidyl isocyanurate production waste liquid comprises TGIC production waste liquid and/or methanol waste liquid, and the method comprises the following steps: sequentially carrying out first acidolysis and intermittent reduced pressure distillation on TGIC production wastewater to obtain condensed water and a light yellow oily substance containing industrial salt; mixing the industrial salt-containing light yellow oily substance with anhydrous methanol, and crystallizing to obtain a methanol solution of inorganic salt and a first oily high-boiling-point substance; sequentially carrying out second acidolysis and first distillation on the methanol waste liquid to obtain anhydrous methanol and a methanol solution of a second oily high-boiling-point substance; carrying out second distillation on the methanol solution of the first oily high-boiling-point substance and/or the methanol solution of the second oily high-boiling-point substance to obtain anhydrous methanol and an oily high-boiling-point substance; and mixing the oily high-boiling-point substance and alkali liquor for cyclization reaction to obtain the epichlorohydrin.
Compared with the prior art, the invention has the following beneficial effects:
1) Since a main raw material in the TGIC production process is Epichlorohydrin (ECH), organic matters contained in the production wastewater are mainly a large amount of epichlorohydrin and complex hydrolysis products thereof due to the traditional production process. Since epichlorohydrin and water form an azeotrope, the wastewater is directly distilled, and a large amount of epichlorohydrin still exists in the distillate. In order to prevent epichlorohydrin from being distilled along with water vapor, the TGIC production wastewater is firstly subjected to acidolysis, the epichlorohydrin is subjected to acidolysis under an acidic condition to obtain high-boiling hydrolysis products such as 1, 3-dichloropropanol, 1-chloropropanediol and glycerinol, and the high-boiling hydrolysis products are difficult to be distilled out along with the water vapor due to a large temperature difference with the boiling point of the water, so that the direct azeotropic distillation of the epichlorohydrin and the water is avoided, the COD in the distilled wastewater is greatly reduced, the treatment efficiency of the wastewater is ensured, and the treated water can reach the national emission standard after being subjected to proper oxidative decomposition treatment;
2) After the acidolysis is finished, if a normal pressure distillation method or a continuous distillation method is adopted, the distillation speed can be reduced due to the balance of saturated vapor pressure in a distillation system, and an intermittent reduced pressure distillation operation technology is adopted, so that the distillation time can be effectively shortened, the distillation efficiency can be improved, the risk that organic matters are evaporated out together can be reduced, and the power consumption of unit volume effluent can be reduced, so that the traditional wastewater treatment cost is reduced, and the industrial economic benefit is met;
3) After the intermittent reduced pressure distillation is finished, the obtained light yellow oily substance containing industrial salt can be precipitated by mixing with anhydrous methanol, and can be reused according with the standard of industrial salt;
4) The oily high-boiling-point substance is treated by alkali liquor, so that the product after acidolysis can be effectively recycled, cyclized again and converted into epoxy chloropropane, the epoxy chloropropane is recycled, the production cost problem caused by raw material loss is reduced, the wastewater treatment cost is greatly reduced, and the industrial economic benefit is compounded;
5) Since the methanol waste liquid mainly contains methanol and about 5% of epichlorohydrin, and since epichlorohydrin and methanol also undergo azeotropic distillation, in order to avoid the above-mentioned azeotropic problem, the methanol waste liquid is first subjected to acidolysis treatment to be converted into high-boiling products such as 1, 3-dichloropropanol, 1-chloropropanediol and glycerol, so that the COD in the distilled methanol is greatly reduced.
Drawings
FIG. 1 is a schematic view showing the process flow of TGIC production wastewater of examples 1 to 2;
FIG. 2 is a schematic view of a process flow of treating the methanol waste liquid shown in examples 3 to 4.
Detailed Description
The invention provides a method for treating triglycidyl isocyanurate production waste liquid, wherein the triglycidyl isocyanurate production waste liquid comprises TGIC production waste liquid and/or methanol waste liquid, and the method comprises the following steps:
sequentially carrying out first acidolysis and intermittent reduced pressure distillation on TGIC production wastewater to obtain condensed water and a light yellow oily substance containing industrial salt;
mixing the industrial salt-containing light yellow oily substance with anhydrous methanol, and crystallizing to obtain a methanol solution of inorganic salt and a first oily high-boiling substance;
sequentially carrying out second acidolysis and first distillation on the methanol waste liquid to obtain anhydrous methanol and a methanol solution of a second oily high-boiling-point substance;
carrying out second distillation on the methanol solution of the first oily high-boiling-point substance and/or the methanol solution of the second oily high-boiling-point substance to obtain anhydrous methanol and an oily high-boiling-point substance;
and mixing the oily high-boiling-point substance and alkali liquor to carry out cyclization reaction to obtain the epichlorohydrin.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
In the present invention, "the triglycidyl isocyanurate production waste liquid includes TGIC production waste water and/or methanol waste liquid" and "the methanol solution of the first oily high boiling substance and/or the methanol solution of the second oily high boiling substance is subjected to second distillation" can be understood as treating TGIC production waste water or methanol waste liquid separately and then treating the obtained methanol solution of the first oily high boiling substance and the obtained methanol solution of the second oily high boiling substance separately; or treating TGIC production wastewater or methanol waste liquid separately, and then mixing the obtained methanol solution of the first oily high-boiling-point substance and the methanol solution of the second oily high-boiling-point substance for treatment.
The TGIC production wastewater is subjected to first acidolysis and intermittent reduced pressure distillation in sequence to obtain condensed water and a light yellow oily substance containing industrial salt.
In the invention, the acid solution used for the first acid hydrolysis is preferably a sulfuric acid solution with the mass concentration of 65-68%; the initial pH value of the first acidolysis is preferably 1-2; the temperature is preferably 50-70 ℃; more preferably 55 to 65 ℃; the time is preferably 1 to 2 hours, more preferably 1.5 hours. In the present invention, the first acid hydrolysis is preferably carried out under stirring, and the stirring conditions in the present invention are not particularly limited, and those well known to those skilled in the art may be used. In the present invention, the heating means for providing the temperature for the first acid hydrolysis is preferably water bath heating.
In the present invention, the first acid hydrolysis process is preferably: under the condition of stirring, dropwise adding a sulfuric acid solution with the mass concentration of 65-68% into the TGIC production wastewater until the pH value of a system is 1-2. The stirring process is not particularly limited, and may be performed by a method known to those skilled in the art.
The invention adopts sulfuric acid solution to carry out acidolysis, thus reducing the cost of wastewater treatment; meanwhile, as for other acids, although hydrochloric acid has relatively good absorption effect on epichlorohydrin, more chloride ions are easily introduced during acidolysis so as to generate a large amount of 1, 3-dichloropropanol with low boiling point, and the 1, 3-dichloropropanol and water azeotropic can cause that the distilled aqueous solution contains a considerable amount of 1, 3-dichloropropanol; nitric acid can be decomposed to generate nitrogen dioxide under the heating condition to form waste gas, so that the difficulty of treating three wastes is increased; the acidity of the phosphoric acid is weaker than that of the sulfuric acid, and the acidolysis efficiency is low; therefore, among the numerous conventional acids, the sulfuric acid is selected to be more effective; meanwhile, the concentrated sulfuric acid is expensive, and the sulfuric acid with the mass concentration of 65-68% is relatively cheap, so that the sulfuric acid with the mass concentration of 65-68% is better in effect, stronger in operability and lower in cost when the first acidolysis is carried out.
In the present invention, the pressure of the batch vacuum distillation is preferably 40 to 45kPa, more preferably 41 to 44kPa, and most preferably 42 to 43kPa; the temperature is preferably 75 to 85 ℃, and more preferably 78 to 82 ℃; the time is preferably 5 to 8 hours, more preferably 6 to 7 hours. In the present invention, the batch vacuum distillation is preferably a one-stage batch vacuum distillation.
The invention reduces the boiling point of the waste liquid after acidolysis by a reduced pressure distillation mode; meanwhile, according to the consideration of thermodynamic equilibrium, the boiling point of the solution changes along with the change of the external pressure, and the forward generation of distillation can be promoted by a reduced pressure distillation mode. By adopting the intermittent reduced pressure distillation mode, the distillation time can be further shortened, the distillation efficiency is improved, the risk that the epichlorohydrin and the hydrolysate thereof are steamed out together is reduced, the power consumption of the effluent in unit volume can be reduced, and the treatment cost of the traditional wastewater is reduced.
After the condensed water is obtained, the invention also preferably comprises the steps of mixing the condensed water with chlorine dioxide solution and then discharging; the mass concentration of the chlorine dioxide solution is preferably 1.0%. In the present invention, the volume ratio of the condensed water to the chlorine dioxide solution is preferably (12 to 22): 1, more preferably 20. In the invention, the mixing temperature is preferably 40 ℃, and the mixing time is preferably 2-3 h; the mixing is preferably carried out under stirring conditions, and the stirring process is not particularly limited in the present invention and may be carried out by a process known to those skilled in the art.
In the invention, the COD content of the condensed water is 5 multiplied by 10 by detecting the COD value of the condensed water 3 ～8×10 3 mg/L, the COD can be further oxidized and decomposed by the treatment of chlorine dioxide solution, so that the COD value reaches 1 multiplied by 10 3 ～2×10 3 The range of mg/L reaches the wastewater discharge standard and is discharged, or the wastewater after oxidative decomposition is recycled as water for TGIC production.
After the industrial salt-containing light yellow oily substance is obtained, the industrial salt-containing light yellow oily substance is mixed with anhydrous methanol for crystallization to obtain a methanol solution of inorganic salt and a first oily high-boiling-point substance.
In the present invention, the volume ratio of the light yellow oil containing industrial salt to anhydrous methanol is preferably 1: (2 to 3), more preferably 1: (2.2 to 2.8), most preferably 1: (2.4-2.6).
In the present invention, the crystallization conditions are not particularly limited, and the inorganic salt may be sufficiently precipitated by using crystallization conditions known to those skilled in the art.
After the crystallization is finished, the method also preferably comprises the steps of filtering, washing and drying which are sequentially carried out; the washing is preferably carried out with absolute ethanol. The filtration and drying process of the present invention is not particularly limited, and may be performed by a process known to those skilled in the art. In the invention, the washed methanol waste liquid is mixed with the methanol solution of the first oily high-boiling-point substance and then recycled.
In the present invention, the inorganic salt can be precipitated by mixing the pale yellow oily substance containing an industrial salt with anhydrous methanol, and can be reused in conformity with the standard as an industrial salt.
According to the invention, the methanol waste liquid is sequentially subjected to second hydrolysis and first distillation to obtain anhydrous methanol and a methanol solution of a second oily high-boiling-point substance.
In the invention, the acid solution used for the second acidolysis is preferably a hydrochloric acid solution with the mass concentration of 30-35%; the initial pH value of the second acidolysis is preferably 2-3, the temperature is preferably 40-50 ℃, and the time is preferably 1-2 h. In the present invention, the second hydrolysis is preferably carried out under stirring conditions, and the stirring conditions in the present invention are not particularly limited, and may be those well known to those skilled in the art.
In the present invention, the second acidolysis is preferably performed under the action of a catalyst; the catalyst is preferably tetraethylammonium chloride; the mass percent of the tetraethylammonium chloride in the methanol waste liquid is preferably 0.0063wt%.
In the present invention, the second acid hydrolysis process is preferably: under the condition of stirring, dropwise adding a hydrochloric acid solution into the methanol waste liquid until the pH value reaches 2-3, and then adding a catalyst to perform secondary acidolysis.
In the invention, hydrochloric acid is selected as the acidolysis agent, so that impurity ions can be prevented from being introduced, and the hydrolysate component of the dichloropropanol can be improved.
In the present invention, the first distillation is preferably atmospheric distillation, and the temperature of the first distillation is preferably 80 to 90 ℃, more preferably 90 ℃; the time is preferably 1 to 3 hours, more preferably 2.5 hours.
In the invention, the anhydrous methanol obtained by the first distillation is subjected to gas chromatography detection, and is recycled (such as recycling) after being qualified, and the anhydrous methanol is subjected to acidolysis and distillation again until being qualified after being unqualified.
After the methanol solution of the first oily high-boiling-point substance and/or the methanol solution of the second oily high-boiling-point substance is obtained, the methanol solution of the first oily high-boiling-point substance and/or the methanol solution of the second oily high-boiling-point substance is subjected to second distillation to obtain anhydrous methanol and oily high-boiling-point substance.
In the present invention, the second distillation is preferably an atmospheric distillation; the temperature of the second distillation is preferably 80-90 ℃, and the time is preferably 1-2 h.
After anhydrous methanol and oily high-boiling-point substances are obtained, the oily high-boiling-point substances and alkali liquor are mixed for cyclization reaction to obtain the epichlorohydrin.
In the present invention, the alkali solution preferably comprises an aqueous solution of sodium hydroxide having a mass concentration of 35 to 45%; the volume ratio of the oily high-boiling substance to the alkali liquor is preferably 1: (1.2 to 1.5), more preferably 1.
In the present invention, the temperature of the cyclization reaction is preferably 75 ℃ and the time is preferably 1.5min.
The following will explain the method for treating the waste liquid from the triglycidyl isocyanurate production provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
As shown in FIG. 1, under stirring, wastewater from 1LTGIC production (COD value 1.85X 10) 5 mg/L, the content of inorganic salt is 3.7wt percent), adding a sulfuric acid solution with the mass concentration of 65 percent dropwise until the pH value is 2, stirring for 2 hours under the condition of water bath at 50 ℃ for acidolysis, and carrying out intermittent reduced pressure distillation (the intermittent reduced pressure distillation is primary reduced pressure distillation under the conditions of 43kPa,75 ℃ and 7 hours) to obtain 0.6L of condensed water (the COD value is 5230 mg/L) and 0.375L of light yellow oily matter containing industrial salt;
heating the 0.6L of condensed water to 40 ℃, slowly dripping 50mL of chlorine dioxide solution with the mass concentration of 1.0%, and continuously keeping the temperature and stirring for 2 hours to obtain water with the COD value of 790mg/L (the water can be recycled or directly discharged);
mixing the industrial salt-containing light yellow oily substance with 1L methanol for crystallization, filtering, washing the filtered solid with methanol, and drying to obtain inorganic salt (41.6 g); the filtrate obtained by filtration is 1.5L of methanol solution of oily high-boiling-point substances;
subjecting the methanol solution of the oily high boiling substance to atmospheric distillation (the conditions of the atmospheric distillation are 1.0atm,90 ℃ C., 2 h) to obtain 1.25L of anhydrous methanol (directly recovered) and 266.9g,0.23L of the oily high boiling substance;
and (3) mixing the oily high waste with 0.3L of sodium hydroxide solution with the mass concentration of 40%, and carrying out cyclization reaction (the temperature is 75 ℃ and the time is 1.5 min) to obtain the epichlorohydrin.
Example 2
As shown in FIG. 1, the wastewater from 10LTGIC production (COD value 1.85X 10) was stirred 5 mg/L, the content of inorganic salt is 3.7wt percent), adding a sulfuric acid solution with the mass concentration of 65 percent dropwise until the pH value is 2, stirring for 1h under the condition of 70 ℃ water bath for acidolysis, and carrying out intermittent reduced pressure distillation (the intermittent reduced pressure distillation is primary reduced pressure distillation under the conditions of 45kPa,85 ℃ and 7 h) to obtain 6.4L of condensed water (the COD value is 7861 mg/L) and 3.35L of light yellow oily matter containing industrial salt;
heating the 6.4L of condensed water to 40 ℃, slowly dripping 0.8L of chlorine dioxide solution with the mass concentration of 1.0%, and continuously keeping the temperature and stirring for 2.5 hours to obtain water with the COD value of 920mg/L (the water can be recycled or directly discharged);
mixing the industrial salt-containing light yellow oily substance with 10L of methanol for crystallization, filtering, washing the solid obtained by filtering with methanol, and drying to obtain inorganic salt (450 g); the filtrate obtained by filtration is 16.5L of methanol solution of oily high-boiling-point substances;
atmospheric distillation of the methanol solution of the oily high boiling substance (the atmospheric distillation conditions are 1.1atm,90 ℃ C., 1 h) to obtain 14.1L of anhydrous methanol and 2617g,2.28L of oily high boiling substance;
and (3) mixing the oily high waste with 2.96L of 38% sodium hydroxide solution by mass, and carrying out cyclization reaction (the temperature is 75 ℃ and the time is 1.5 min) to obtain the epichlorohydrin.
Example 3
As shown in fig. 2, under the condition of stirring, hydrochloric acid with the mass concentration of 32% is dripped into 1L of methanol waste liquid (the content of epichlorohydrin is 4.58 wt%) until the pH value is 3, 0.05g of tetraethylammonium chloride is added, the mixture is stirred for 2 hours under the condition of water bath at 40 ℃ for acidolysis, and then the mixture is distilled at the temperature of 65 ℃ under normal pressure for 3 hours to obtain anhydrous methanol (0.87L, the content of epichlorohydrin is 20ppm, and the mass content of methanol is 99.6%) and a methanol solution (0.11L) of oily high boiling substances;
the methanol solution of the oily high-boiling-point substance is subjected to atmospheric distillation (the conditions of the atmospheric distillation are 90 ℃ and 2 hours), so that 0.065L of anhydrous methanol and 0.04L of oily high-boiling-point substance are obtained;
and (3) mixing the oily high waste with 0.55L of 40% sodium hydroxide solution by mass, and carrying out cyclization reaction (the temperature is 75 ℃ and the time is 1.5 min) to obtain the epichlorohydrin.
Example 4
As shown in fig. 2, under the condition of stirring, hydrochloric acid with the mass concentration of 32% is dripped into 10L of methanol waste liquid (the content of epichlorohydrin is 4.58 wt%) until the pH value is 3, 0.3g of tetraethylammonium chloride is added, the mixture is stirred for 1h under the condition of water bath at 50 ℃ for acidolysis, and then the mixture is distilled at the temperature of 65 ℃ under normal pressure for 2.5h to obtain absolute methanol (8.9L, the content of epichlorohydrin is 60ppm, and the mass content of methanol is 99.3%) and methanol solution (0.95L) of oily high boiling substances;
the methanol solution of the oily high boiling substance is subjected to atmospheric distillation (the atmospheric distillation condition is 85 ℃, and 1 hour), so that 0.49L of anhydrous methanol and 0.45L of oily high boiling substance are obtained;
and (3) mixing the oily high waste with 0.60L of 38% sodium hydroxide solution by mass, and carrying out cyclization reaction (the temperature is 75 ℃ and the time is 1.5 min) to obtain the epichlorohydrin.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A treatment method of triglycidyl isocyanurate production waste liquid comprises TGIC production waste liquid and/or methanol waste liquid, and is characterized by comprising the following steps:
sequentially carrying out first acidolysis and intermittent reduced pressure distillation on the TGIC production wastewater to obtain condensed water and a light yellow oily substance containing industrial salt;
mixing the industrial salt-containing light yellow oily substance with anhydrous methanol, and crystallizing to obtain a methanol solution of inorganic salt and a first oily high-boiling substance;
sequentially carrying out second acidolysis and first distillation on the methanol waste liquid to obtain anhydrous methanol and a methanol solution of a second oily high-boiling-point substance;
carrying out second distillation on the methanol solution of the first oily high-boiling-point substance and/or the methanol solution of the second oily high-boiling-point substance to obtain anhydrous methanol and oily high-boiling-point substances;
mixing the oily high-boiling-point substance and alkali liquor to carry out cyclization reaction to obtain epoxy chloropropane;
the TGIC production wastewater is TGIC production wastewater containing industrial waste salt obtained while preparing a TGIC crude product in the traditional TGIC production process taking water as a solvent;
the methanol waste liquid is generated in the process of recrystallizing a TGIC crude product with a hot methanol solution to obtain a TGIC refined product in the traditional TGIC production process with water as a solvent.
2. The treatment method as claimed in claim 1, wherein the acid solution used for the first acid hydrolysis is a sulfuric acid solution having a mass concentration of 65 to 68%;
the initial pH of the first acidolysis is = 1-2, the temperature is 50-70 ℃, and the time is 1-2 h.
3. The process according to claim 1, wherein the pressure of the batch-type reduced pressure distillation is 40 to 45kPa, the temperature is 75 to 85 ℃ and the time is 5 to 8 hours.
4. The treatment method according to claim 1, wherein after the condensed water is obtained, the condensed water is mixed with a chlorine dioxide solution and then discharged;
the mass concentration of the chlorine dioxide solution is 1.0%.
5. The process of claim 1, wherein the ratio of the industrial salt-containing pale yellow oil to the anhydrous methanol is from 1: (2-3).
6. The treatment method according to claim 1, wherein the acid solution used for the second acidolysis is a hydrochloric acid solution with a mass concentration of 30-35%;
the initial pH of the second acidolysis is = 2-3, the temperature is 40-50 ℃, and the time is 1-2 h.
7. The process according to claim 1, characterized in that the temperature of the first distillation is between 80 and 90 ℃ and the time is between 1 and 3 hours.
8. The process of claim 1, wherein the second distillation is an atmospheric distillation; the temperature of the second distillation is 80-90 ℃, and the time is 1-2 h.
9. The process of claim 1, wherein the alkali solution comprises an aqueous solution of sodium hydroxide having a mass concentration of 35 to 45%;
the volume ratio of the oily high-boiling residue to the alkali liquor is 1: (1.2-1.5).
10. The process according to claim 1, wherein the temperature of the cyclization reaction is 75 ℃ and the time is 1.5min.
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| JP2002322105A (en) * | 2001-04-26 | 2002-11-08 | Showa Denko Kk | Preparation method for 2,3-dichloro-1-propanol and epichlorohydrin |
| JP2009263338A (en) * | 2008-03-12 | 2009-11-12 | Daiso Co Ltd | Novel manufacturing method of epichlorohydrin |
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| CN111018665A (en) * | 2019-12-17 | 2020-04-17 | 山东民基化工有限公司 | Method for recycling trichloropropane in epichlorohydrin heavy component |
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| JP2002322105A (en) * | 2001-04-26 | 2002-11-08 | Showa Denko Kk | Preparation method for 2,3-dichloro-1-propanol and epichlorohydrin |
| JP2009263338A (en) * | 2008-03-12 | 2009-11-12 | Daiso Co Ltd | Novel manufacturing method of epichlorohydrin |
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