CN110980847A - Treatment and recovery system and method for waste alkali in methane chloride production - Google Patents
Treatment and recovery system and method for waste alkali in methane chloride production Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention relates to a treatment and recovery system and a method for producing waste alkali by methane chloride, belonging to the technical field of wastewater treatment and recovery, and the method comprises the following steps: feeding the methane chloride waste alkaline water into a stripping tower for steam stripping to obtain waste alkaline from which most of methane chloride is removed, and feeding the waste alkaline into a triple-effect evaporator; dissolving the evaporated solid waste salt in a dissolving tank, filtering by using a filter, feeding the filtered solution into a chlor-alkali workshop to be used as a raw material, and filtering to obtain the waste salt containing NaOH, NaCl and Na2CO3The solution of (4), wherein the organic matter content is less than 1ppm by mass. In the invention, the solution obtained by the steps of steam stripping, evaporation, dissolution, filtration and the like of the waste alkaline water produced by the methane chloride can be used as a raw material of the chlor-alkali industry, thus changing waste into valuable; through resource utilization of waste alkali in production, the treatment cost of waste water is reducedThe method overcomes the defects of large investment and large environmental pressure of the existing water treatment.
Description
Technical Field
The invention relates to a treatment and recovery system and a treatment and recovery method for waste alkali produced in methane chloride production, and belongs to the technical field of wastewater treatment and recovery.
Background
Methane chloride (including methyl chloride, methylene chloride, chloroform and carbon tetrachloride) is an important chemical raw material, and many high-salt and high-Chemical Oxygen Demand (COD) alkaline waters are produced in the production process of the methane chloride. For the high-salt and high-COD alkaline water, domestic enterprises mostly adopt a method of firstly pretreating the wastewater by using a multi-effect evaporation method and then biochemically treating the evaporated condensate water. The method for treating the wastewater can generate a large amount of crystal salt in the evaporation process, and the crystal salt contains a large amount of pollutants which can only be used as dangerous solid waste under most conditions, so that qualified units are required to carry out harmless treatment, the treatment cost is high, and the operation cost of enterprises is greatly increased.
In China, some enterprises adopt a high-temperature incineration method, but the method has high equipment and treatment cost, and can convert organic matters in waste salt into more complex organic matter residual components, such as dioxin-like organic matters and the like. Currently, with the stricter environmental requirements, it is important to find a method for recycling the spent caustic soda.
Sodium chloride is used as a raw material in the chlor-alkali industry to produce caustic soda and chlorine, 32 percent of industrial sodium hydroxide can be obtained by an aqueous solution of the sodium chloride through ion membrane electrolysis, but the ion membrane electrolysis has higher requirements on the water quality of the inlet tank brine, and the Total Organic Carbon (TOC) index of the inlet tank brine is required to be less than 10 mg/L. If the high-salt and high-COD alkali waste can meet the requirements of the chlor-alkali industry on raw materials through treatment, the alkali waste can be changed into valuable.
Chinese patent CN102689975A discloses a method for treating high-salinity wastewater as a resource, which is a method for removing organic pollutants contained in high-salinity wastewater by a catalytic wet peroxide oxidation method and optimizes the adding amount and adding mode of a catalyst and an oxidant. However, the method needs to add an oxidant and a catalyst, increases the operation cost, brings uncontrollable factors to the use of subsequent salt for chlor-alkali industry, and is not known whether the method has a continuous and stable treatment effect in industrial production.
Chinese patent CN109579025A discloses an efficient melting and incinerating device for industrial waste salt, which adopts a method of an efficient melting and incinerating furnace to incinerate solid waste salt at high temperature, most organic matters can be decomposed at high temperature, but the equipment and operation cost are high, and the specific technical indexes reached by the waste salt after treatment are not disclosed.
Disclosure of Invention
Aiming at the defects of the existing wastewater treatment method, the invention provides a system and a method for treating and recycling waste alkali produced in methane chloride, which overcome the defects of large investment, high operation cost and unrealized resource utilization in the wastewater treatment process.
The invention adopts the following technical scheme:
on one hand, the invention provides a treatment and recovery system for waste alkali produced in methane chloride production, which comprises a waste alkali liquid tank, a stripping tower, a three-effect evaporator, a dissolving tank and a filter, which are connected in sequence;
the waste alkali liquid tank is used for containing methane chloride waste alkali water, the outlet at the bottom of the tower of the stripping tower is connected with the inlet of the triple-effect evaporator, the bottom outlet of the triple-effect evaporator is connected with the inlet of the dissolving tank, the upper outlet of the triple-effect evaporator is connected with the existing water treatment device, the outlet of the dissolving tank is connected with the outlet of the filter, and the methane chloride waste water liquid enters the chlorine alkali brine process after being filtered by the filter.
Preferably, the outlet of the tower top of the stripping tower is also connected with a tower top condenser, the outlet of the tower top condenser is connected with a phase separation tank, the outlet of the upper part of the phase separation tank is connected with the inlet of the stripping tower and returns to the inlet of the stripping tower for retreatment, and the outlet of the lower part of the phase separation tank is connected with a wet regeneration tank.
The stripping tower, the triple-effect evaporator, the dissolving tank, the filter, the tower top condenser and the phase separation tank used in the invention are all existing equipment and can be purchased from the market, and the details are not repeated here.
On the other hand, the invention also provides a method for treating and recycling the waste alkali generated in the production of methane chloride by adopting the system, which comprises the following steps:
(1) and (2) feeding the methane chloride alkali waste water into a waste alkali water tank, and feeding the methane chloride alkali waste water into a stripping tower through a stripping tower feeding pump for stripping, wherein the methane chloride alkali waste water comprises the following components: the mass content of the organic matter is 2000-5000ppm, the sodium chloride is 5-10 wt%, the sodium carbonate is 3-5 wt%, the sodium hydroxide is 2-5 wt%, and the balance is water;
(2) steam is introduced into the stripping tower, the waste alkali of the methane chloride is extracted from the top of the stripping tower along with the steam, and the waste alkali containing a small amount of methane chloride lower than 100ppm enters a triple-effect evaporator from an outlet at the bottom of the stripping tower;
(3) dissolving the solid waste salt evaporated by the triple-effect evaporator by a dissolving tank, filtering by a filter, feeding the filtered solution into a chlor-alkali workshop to be used as a raw material, and filtering to obtain the product containing NaOH, NaCl and Na2CO3The solution of (4), wherein the organic matter content is less than 1ppm by mass.
Usually, the content of organic matters entering the electrolytic bath brine in the chlor-alkali industry is required to be less than 10ppm, and NaCl which is a raw material of the chlor-alkali industry and is a substance obtained after the process is filtered is NaOH and Na2CO3The additive is added as an auxiliary material in a chlor-alkali working section, so that the addition of auxiliary materials in the later period can be reduced, and the process in the chlor-alkali industry is facilitated.
Preferably, steam is introduced into the stripping tower in the step (2), the gas phase at the top of the stripping tower is condensed by a tower top condenser, the condensed water and the mixed liquid containing methane chloride enter a phase separation tank, the water discharged from an upper outlet of the phase separation tank and a small amount of methane chloride dissolved in the water return to an upper inlet of the stripping tower for reprocessing, the mixed liquid containing methane chloride discharged from a lower outlet of the phase separation tank enters a wet regeneration tank for recycling after drying treatment, in the phase separation tank, the mixed liquid containing water and methane chloride is layered, the water is on the upper part, the methane chloride is on the lower part, the main component of the mixed liquid on the lower part is methane chloride, and the mixed liquid enters a.
Preferably, steam of 0.3-0.8MPa is introduced into the stripping tower in the step (2), and the methane chloride waste alkaline water is heated to 80-90 ℃ on the stripping tower through the steam.
Preferably, the gas phase of the stripper is condensed to 35 ℃ to 40 ℃ by an overhead condenser.
Preferably, the mass content of organic matters in the waste alkali of the methane chloride discharged from the bottom of the stripping tower is 50-100 ppm;
preferably, tower bottom liquid discharged from the bottom of the stripping tower enters a triple-effect evaporator, the triple-effect evaporator heats the tower bottom liquid to 80-110 ℃, the tower bottom liquid is concentrated and then subjected to solid-liquid separation, the mass content of separated solid waste salt organic matters is less than 5ppm, the solid waste salt after the solid-liquid separation sequentially enters a dissolving tank for dissolving, a filter is used for filtering, the solid waste salt is sent to a chlor-alkali workshop through a pipeline to be used as a raw material, condensed water generated by the triple-effect evaporator enters an existing water treatment system, the main component of the substance of the existing water treatment system is water containing a small amount of organic matters, and the discharge standard can be achieved by slightly processing the condensed water.
Preferably, the filter adopts the prior art, and the filter element adopts glass fiber.
The invention is not described in detail in the prior art.
The invention has the beneficial effects that:
1) the solution obtained by the steps of steam stripping, evaporation, dissolution, filtration and the like of the methane chloride waste alkaline water can be used as a raw material of the chlor-alkali industry, thereby changing waste into valuable.
2) The invention reduces the treatment cost of the waste water, has small investment and large environmental pressure by resource utilization of the production waste alkali.
Drawings
FIG. 1 is a process flow diagram of a treatment and recovery system for waste alkali in methane chloride production according to the present invention;
wherein, the device comprises a waste alkali liquor tank 1, a stripping tower 2, a tower top condenser 3, a phase separation tank 4, a triple-effect evaporator 5, a dissolving tank 6 and a filter 7.
The specific implementation mode is as follows:
in order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific examples, but not limited thereto, and the present invention is not described in detail and is in accordance with the conventional techniques in the art.
The methods mentioned in the following examples are conventional unless otherwise specified, and the reagents, equipment and materials, which are conventional in the art, are commercially available.
Example 1:
a processing and recycling system for waste alkali produced in methane chloride production is shown in figure 1 and comprises a waste alkali liquid tank 1, a stripping tower 2, a triple-effect evaporator 5, a dissolving tank 6 and a filter 7 which are connected in sequence;
the waste alkali liquor tank 1 is used for containing methane chloride waste alkali water, a tower bottom outlet of the stripping tower 2 is connected with an inlet of a triple-effect evaporator 5, a bottom outlet of the triple-effect evaporator 5 is connected with an inlet of a dissolving tank 6, an upper outlet of the triple-effect evaporator 5 is connected with an existing water treatment device, an outlet of the dissolving tank 6 is connected with an outlet of a filter 7, and the methane chloride waste water liquid is filtered by the filter 7 and then enters a chlor-alkali brine process;
the outlet of the top of the stripping tower 2 is also connected with a top condenser 3, the outlet of the top condenser 3 is connected with a phase separation tank 4, the outlet of the upper part of the phase separation tank 4 is connected with the inlet of the stripping tower 2, and the outlet of the lower part of the phase separation tank 4 is connected with the existing wet regeneration tank.
Example 2:
a method for treating and recovering waste alkali generated in methane chloride production comprises the following steps:
(1) the method comprises the following steps of (1) feeding methane chloride waste alkaline water into a waste alkaline liquid tank 1, and feeding the methane chloride waste alkaline water into a stripping tower 2 through a stripping tower feeding pump for stripping, wherein the methane chloride waste alkaline water comprises the following components: the mass content of the organic matter is 2000-5000ppm, the sodium chloride is 5-10 wt%, the sodium carbonate is 3-5 wt%, the sodium hydroxide is 2-5 wt%, and the balance is water;
(2) steam of 0.3MPa is introduced into the stripping tower, the waste alkali water of the methane chloride is heated to 85 ℃ on the stripping tower 2 through the steam, the waste alkali of the methane chloride is extracted from the top of the stripping tower along with the steam, a small amount of waste alkali of the methane chloride with the organic matter content of less than 100ppm is discharged from an outlet at the bottom of the stripping tower and is sent into a triple-effect evaporator 5 through a pump;
the gas phase at the top of the stripping tower 2 is condensed to 35 ℃ through a condenser 3 at the top of the stripping tower, the water and a small amount of methane chloride mixed liquor discharged from the condenser enter a phase separation tank 4, the water discharged from the upper part of the phase separation tank 4 returns to an inlet at the upper part of the stripping tower 2 for retreatment, and the methane chloride mixed liquor discharged from the lower part of the phase separation tank 4 enters a wet regeneration tank for drying treatment and recycling;
(3) heating the triple-effect evaporator 5 to 80 ℃, concentrating tower bottom liquid, performing solid-liquid separation, enabling the mass content of separated solid waste salt organic matters to be less than 5ppm, enabling condensed water generated by the triple-effect evaporator to enter an existing water treatment system, and enabling the solid-liquid to be solid-liquidDissolving the separated solid waste salt in a dissolving tank 6, filtering by a filter 7, feeding the filtered solution into a chlor-alkali workshop through a pipeline to be used as a raw material, and filtering to obtain the waste salt containing NaOH, NaCl and Na2CO3The solution of (4), wherein the organic matter content is less than 1ppm by mass.
Example 3:
a method for treating and recovering waste alkali generated in methane chloride production comprises the following steps:
(1) the method comprises the following steps of (1) feeding methane chloride waste alkaline water into a waste alkaline liquid tank 1, and feeding the methane chloride waste alkaline water into a stripping tower 2 through a stripping tower feeding pump for stripping, wherein the methane chloride waste alkaline water comprises the following components: 3000ppm of organic matter mass content 2000-sodium chloride, 5-10% wt of sodium chloride, 3-5% wt of sodium carbonate, 2-5% wt of sodium hydroxide and the balance of water;
(2) steam of 0.5MPa is introduced into the stripping tower, the waste alkali water of the methane chloride is heated to 85 ℃ on the stripping tower 2 through the steam, the waste alkali of the methane chloride is extracted from the top of the stripping tower along with the steam, the tower bottom liquid with the organic matter content of less than 100ppm is discharged from an outlet at the bottom of the tower bottom, and the tower bottom liquid is pumped into a triple-effect evaporator 5;
the gas phase of the stripping tower 2 is condensed to 40 ℃ through a top condenser 3, water and a small amount of methane chloride mixed liquor discharged from the condenser enter a phase separation tank 4, water discharged from the upper part of the phase separation tank 4 returns to an inlet at the upper part of the stripping tower 2 for retreatment, and the methane chloride mixed liquor discharged from the lower part of the phase separation tank 4 enters a wet regeneration tank for drying treatment and recycling;
(3) heating a triple-effect evaporator 5 to 100 ℃, concentrating tower bottom liquid, performing solid-liquid separation, enabling the mass content of the separated solid waste salt organic matters to be less than 5ppm, enabling condensed water generated by the triple-effect evaporator 5 to enter an existing water treatment system, dissolving the solid waste salt subjected to solid-liquid separation by a dissolving tank 6, filtering by a filter 7, enabling the filtered solution to enter a chlor-alkali workshop through a pipeline for use as a raw material, and filtering to obtain a concentrated solution containing NaOH, NaCl and Na2CO3The solution of (4), wherein the organic matter content is less than 1ppm by mass.
Example 4:
a method for treating and recovering waste alkali generated in methane chloride production comprises the following steps:
(1) the method comprises the following steps of (1) feeding methane chloride waste alkaline water into a waste alkaline liquid tank 1, and feeding the methane chloride waste alkaline water into a stripping tower 2 through a stripping tower feeding pump for stripping, wherein the methane chloride waste alkaline water comprises the following components: the organic matter mass content is 4000-5000ppm, the sodium chloride is 5-10 wt%, the sodium carbonate is 3-5 wt%, the sodium hydroxide is 2-5 wt%, and the balance is water;
(2) steam of 0.8MPa is introduced into the stripping tower, the waste alkali water of the methane chloride is heated to 90 ℃ on the stripping tower 2 through the steam, the waste alkali of the methane chloride is extracted from the top of the stripping tower along with the steam, the tower bottom liquid with the organic matter content of less than 100ppm is discharged from an outlet at the bottom of the tower bottom, and the tower bottom liquid is pumped into a triple-effect evaporator 5;
the gas phase of the stripping tower is condensed to 40 ℃ through a condenser 3 at the top of the tower, the water and a small amount of methane chloride mixed liquor discharged from the condenser enter a phase separation tank 4, the water discharged from the upper part of the phase separation tank 4 returns to an inlet at the upper part of the stripping tower 2 for retreatment, and the methane chloride mixed liquor discharged from the lower part of the phase separation tank 4 enters a wet regeneration tank for drying treatment and recycling;
(3) heating a triple-effect evaporator 5 to 110 ℃, concentrating tower bottom liquid, performing solid-liquid separation, enabling the mass content of the separated solid waste salt organic matters to be less than 5ppm, enabling condensed water generated by the triple-effect evaporator 5 to enter an existing water treatment system, dissolving the solid waste salt subjected to solid-liquid separation by a dissolving tank 6, filtering by a filter 7, enabling the filtered solution to enter a chlor-alkali workshop through a pipeline for use as a raw material, and filtering to obtain a concentrated solution containing NaOH, NaCl and Na2CO3The solution of (4), wherein the organic matter content is less than 1ppm by mass.
In the embodiments 2-4 of the present invention, the substances obtained by the final filtration all contain NaOH, NaCl and Na2CO3The solution of (1) wherein the organic matter content is less than 1ppm, NaCl is a raw material of chlor-alkali industry, NaOH, Na2CO3The auxiliary material is added in a chlor-alkali working section, so that the addition of auxiliary materials in the later period can be reduced, the mass content of organic matters meets the requirement of the content of the organic matters of brine entering an electrolytic cell in the chlor-alkali industry, the intermediate product is divided into two parts, one part is a methane chloride mixed solution positioned below a phase separation tank, and the dried product enters a methane chloride production process and returns to the methane chloride production processThe other part of the water containing a small amount of organic matters generated by the triple-effect evaporator is treated by the existing water treatment system to reach the discharge standard.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. A treatment and recovery system for waste alkali in methane chloride production is characterized by comprising a waste alkali liquid tank, a stripping tower, a three-effect evaporator, a dissolving tank and a filter which are sequentially connected;
the waste alkali liquid tank is used for containing methane chloride waste alkali water, the outlet at the bottom of the tower of the stripping tower is connected with the inlet of the triple-effect evaporator, the bottom outlet of the triple-effect evaporator is connected with the inlet of the dissolving tank, the upper outlet of the triple-effect evaporator is connected with the existing water treatment device, the outlet of the dissolving tank is connected with the outlet of the filter, and the methane chloride waste water liquid enters the chlorine alkali brine process after being filtered by the filter.
2. The system for treating and recovering the waste alkali from methane chloride production according to claim 1, wherein the outlet of the tower top of the stripping tower is further connected with a tower top condenser, the outlet of the tower top condenser is connected with a phase separation tank, the outlet of the upper part of the phase separation tank is connected with the inlet of the stripping tower and returns to the inlet of the stripping tower for retreatment, and the outlet of the lower part of the phase separation tank is connected with a wet regeneration tank.
3. A method for treating and recovering the waste alkali generated in the production of methane chloride by adopting the system of claim 2, which comprises the following steps:
(1) and (2) feeding the methane chloride waste alkaline water into a waste alkaline liquid tank, and feeding the methane chloride waste alkaline water into a stripping tower for stripping, wherein the methane chloride waste alkaline water comprises the following components: the mass content of the organic matter is 2000-5000ppm, the sodium chloride is 5-10 wt%, the sodium carbonate is 3-5 wt%, the sodium hydroxide is 2-5 wt%, and the balance is water;
(2) steam is introduced into the stripping tower, the waste alkali of the methane chloride is extracted from the top of the stripping tower along with the steam, and the waste alkali containing the methane chloride lower than 100ppm enters a triple-effect evaporator from an outlet at the bottom of the stripping tower;
(3) dissolving the evaporated solid waste salt in a dissolving tank, filtering by using a filter, feeding the filtered solution into a chlor-alkali workshop to be used as a raw material, and filtering to obtain the waste salt containing NaOH, NaCl and Na2CO3The solution of (4), wherein the organic matter content is less than 1ppm by mass.
4. The method for treating and recovering alkali waste from methane chloride production according to claim 3, wherein in the step (2), steam is introduced into the stripping tower, the gas phase at the top of the stripping tower is condensed by a condenser at the top of the stripping tower, the condensed water and the mixed solution containing methane chloride enter a phase separation tank, the water discharged from an outlet at the upper part of the phase separation tank and the methane chloride dissolved in the water return to an inlet at the upper part of the stripping tower for reprocessing, and the mixed solution of methane chloride discharged from an outlet at the lower part of the phase separation tank enters a wet regeneration tank for drying treatment and then recycling.
5. The method for treating and recovering the waste alkali generated in the production of the methane chloride according to claim 4, wherein steam with pressure of 0.3-0.8MPa is introduced into the stripping tower in the step (2), and the waste alkali generated in the production of the methane chloride is heated to 80-90 ℃ by the steam on the stripping tower.
6. The method for treating and recovering the waste alkali from methane chloride production according to claim 5, wherein the gas phase in the stripping tower is condensed to 35-40 ℃ by an overhead condenser.
7. The method for treating and recovering the waste alkali from methane chloride production according to claim 6, wherein the mass content of organic matters in the tower bottom liquid discharged from the bottom of the stripping tower is 50-100 ppm.
8. The method for treating and recovering the waste alkali produced in the production of the methane chloride as claimed in claim 7, wherein the tower bottom liquid discharged from the bottom of the stripping tower enters a triple-effect evaporator, the triple-effect evaporator heats the tower bottom liquid to 80-110 ℃, the tower bottom liquid is concentrated and then subjected to solid-liquid separation, the mass content of the separated solid waste salt organic matters is less than 5ppm, the solid waste salt after the solid-liquid separation sequentially enters a dissolving tank for dissolution, is filtered by a filter and is sent to a chlor-alkali workshop through a pipeline to be used as a raw material, and the condensed water produced by the triple-effect evaporator enters an existing water treatment system.
9. The method for treating and recovering the waste alkali from methane chloride production according to claim 8, wherein the filter element is made of glass fiber.
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| CN112403134A (en) * | 2020-12-02 | 2021-02-26 | 中国成达工程有限公司 | System and method for treating sublimate of electrolytic magnesium anode |
| CN114773214A (en) * | 2022-03-30 | 2022-07-22 | 山东蓝湾新材料有限公司 | Industrial preparation method of acryloyloxyethyl trimethyl ammonium chloride |
| CN114773214B (en) * | 2022-03-30 | 2023-11-17 | 山东蓝湾新材料有限公司 | Industrial preparation method of acryloyloxyethyl trimethyl ammonium chloride |
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