CN111333249A - Method for treating waste liquid containing chlorinated organic matter - Google Patents
Method for treating waste liquid containing chlorinated organic matter Download PDFInfo
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- CN111333249A CN111333249A CN202010181987.7A CN202010181987A CN111333249A CN 111333249 A CN111333249 A CN 111333249A CN 202010181987 A CN202010181987 A CN 202010181987A CN 111333249 A CN111333249 A CN 111333249A
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- 239000007788 liquid Substances 0.000 title claims abstract description 103
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000005416 organic matter Substances 0.000 title claims abstract description 29
- 239000000460 chlorine Substances 0.000 claims abstract description 79
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 79
- 239000010815 organic waste Substances 0.000 claims abstract description 60
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 41
- 229910001504 inorganic chloride Inorganic materials 0.000 claims abstract description 40
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 30
- 239000012074 organic phase Substances 0.000 claims abstract description 29
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000011033 desalting Methods 0.000 claims abstract description 16
- 230000007935 neutral effect Effects 0.000 claims abstract description 16
- 239000012071 phase Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 131
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 51
- 230000001105 regulatory effect Effects 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000008346 aqueous phase Substances 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000012528 membrane Substances 0.000 claims description 21
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 239000003011 anion exchange membrane Substances 0.000 claims description 11
- 238000005341 cation exchange Methods 0.000 claims description 11
- 150000003841 chloride salts Chemical class 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 238000009279 wet oxidation reaction Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 2
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- -1 hydrogen Chemical class 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 7
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 35
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 34
- 239000011780 sodium chloride Substances 0.000 description 14
- 239000001103 potassium chloride Substances 0.000 description 12
- 235000011164 potassium chloride Nutrition 0.000 description 12
- 239000003513 alkali Substances 0.000 description 9
- 239000002562 thickening agent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 6
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- 238000006731 degradation reaction Methods 0.000 description 5
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- 239000010865 sewage Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000004064 recycling Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a method for treating chlorinated organic matter-containing waste liquid, which belongs to the technical field of organic matter waste liquid treatment, wherein the organic matter waste liquid is firstly reacted with a chlorine substituting agent to convert organic chlorine in the organic matter waste liquid into inorganic chloride; then, after the pH value of the organic waste liquid containing inorganic chloride is adjusted to be neutral, separating to obtain a water phase solution dissolved in water and an organic phase solution not dissolved in water; desalting the water phase solution, and separating to obtain inorganic chloride concentrated solution and dechlorination solution; the organic phase solution and dechlorination solution are degraded through oxidation reaction. The method for treating the chlorinated organic matter-containing waste liquid provided by the invention avoids dioxin and hydrogen chloride formed in the organic matter waste liquid treatment process, corrosion of equipment and environmental pollution.
Description
Technical Field
The invention belongs to the technical field of organic matter waste liquid treatment, and particularly relates to a method for treating chlorinated organic matter-containing waste liquid.
Background
The chlorinated organic compounds have the characteristics of photo-thermal stability, biological toxicity, pharmacological action and the like, and are widely applied to the fields of chemical production of basic chemicals, agricultural medicines, flame retardants, high polymer materials, dyes, daily chemicals and the like. The production of the chemical industry can generate a large amount of waste liquid containing chlorinated organic matters, and the waste liquid has the characteristics of high COD (chemical oxygen demand), high biotoxicity, difficult degradation and the like. In the prior art, the waste liquid containing chlorinated organic matters is directly treated, dioxin and hydrogen chloride are formed in the treatment process, equipment is corroded, the environment is polluted, a large amount of waste salt is generated and is treated as solid waste, or the waste salt is further purified and treated for recycling, and the cost is high.
Disclosure of Invention
The invention aims to provide a method for treating a chlorinated organic matter-containing waste liquid, and aims to solve the problems that dioxin and hydrogen chloride are formed in the treatment process of the chlorinated organic matter-containing waste liquid, equipment is corroded, the environment is polluted, a large amount of waste salt is generated and is treated as solid waste, or is further purified and treated for resource utilization, and the cost is high in the prior art.
In order to achieve the purpose, the invention adopts the technical scheme that: provides a method for treating chlorinated organic matter-containing waste liquid, which comprises the following steps:
reacting the organic waste liquid with a chlorine substituting agent, and converting organic chlorine in the organic waste liquid into inorganic chloride;
adjusting the pH value of the organic waste liquid containing inorganic chloride to be neutral, and separating to obtain a water-soluble aqueous phase solution and a water-insoluble organic phase solution;
desalting the water phase solution, and separating to obtain inorganic chloride concentrated solution and dechlorination solution;
the organic phase solution and dechlorination solution are degraded through oxidation reaction.
As another embodiment of the present application, the chlorine substitution agent is NaOH or KOH or H2With NaOH or H2With KOH, H2Used in combination with a Ni-based catalyst or a Pb-based catalyst.
As another embodiment of the application, the reaction temperature of the reaction of the organic waste liquid and the chlorine substituting agent is controlled to be 60-200 ℃, the pressure is controlled to be 0.1-2.0Mpa, and the reaction time is 0.5-2 h.
As another embodiment of the present application, the molar ratio of NaOH or KOH to chlorine in the organic waste liquid is 1:1 to 1: 1.2.
As another example of the present application, H2The mol ratio of the organic waste liquid to the chlorine in the organic waste liquid is 2:1-2.2:1, the mol ratio of the Ni in the Ni-based catalyst to the chlorine in the organic waste liquid is 1:45-1:90, and the mol ratio of the Pb in the Pb-based catalyst to the chlorine in the organic waste liquid is 1: 500-1: 800.
as another example of the present application, the aqueous phase solution is subjected to desalting treatment by passing through a separation membrane, and the inorganic chloride salt concentrate is passed through the separation membrane.
As another embodiment of the present application, the separation membrane includes a cation exchange membrane and an anion exchange membrane, a channel is disposed between the anion exchange membrane and the cation exchange membrane, and ions in the aqueous solution move toward the anion exchange membrane or the cation exchange membrane under the action of the adjusting voltage.
As another embodiment of the present application, the voltage regulation process for regulating the voltage includes the following steps:
gradually increasing the regulating voltage, wherein the regulating current is increased along with the increase of the regulating voltage;
when the regulating voltage is continuously increased and the regulating current is slowly increased, stopping increasing the regulating voltage and keeping the regulating voltage stable;
when the regulated current begins to drop, the regulated voltage is gradually reduced as the regulated current drops.
As another example of the present application, the oxidation reaction is a burning oxidation reaction, a supercritical oxidation reaction, or a wet oxidation reaction.
As another embodiment of the present application, the concentrated solution of inorganic chloride salt is evaporated and crystallized to obtain a mother solution of crystallization, the mother solution of crystallization is settled, and the concentrated solution of crystallization salt obtained by settling is dehydrated to obtain solid salt.
The method for treating the chlorinated organic matter-containing waste liquid has the beneficial effects that: compared with the prior art, the method for treating the chlorinated organic matter-containing waste liquid comprises the steps of firstly converting organic chlorine in the organic matter waste liquid into inorganic chloride by using a chlorine substitute, adjusting the pH value of the organic matter waste liquid containing the inorganic chloride to be neutral, separating a water-soluble aqueous phase solution from a water-insoluble organic phase solution, and performing dechlorination and separation on the aqueous phase solution to obtain an inorganic chloride concentrated solution and a dechlorination solution, wherein the inorganic chloride concentrated solution can be used for extracting the inorganic chloride, and the dechlorination solution and the organic phase solution are subjected to oxidation reaction degradation. The chlorine element is the main reason for forming dioxin and hydrogen chloride in the treatment process, the invention firstly carries out chlorine substitution reaction on the organic waste liquid, then adjusts the organic waste liquid containing inorganic chloride to be neutral, so that the water phase solution is separated from the organic phase solution, the chlorine element is dissolved in the water phase solution, the organic phase solution is directly degraded by oxidation reaction, and the water phase solution is firstly dechlorinated and then degraded by oxidation reaction, thereby avoiding forming dioxin and hydrogen chloride in the treatment process, corroding equipment and polluting the environment, and simultaneously, the inorganic chloride concentrated solution can be reused, and resource waste is avoided.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of a method for treating a chlorinated organic compound-containing waste liquid according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The reaction principle of the reaction of the organic waste liquid and the chlorine substituting agent is as follows:
chlorine element in the chlorinated organic matter is in an organic state, is connected with the main body in a covalent bond form and cannot be directly removed.
When the chlorine substituting agent is NaOH or KOH, OH-in the alkali MOH attacks the R-Cl bond of a chlorinated organic substance RCl in the reaction to carry out nucleophilic substitution so as to generate a chlorine-free organic substance RM and a chloride salt MCl, wherein the reaction formula is as follows:
RCl+MOH→RM+MCl
when the chlorine substituent is H2With NaOH or H2And KOH, a Ni-based catalyst or a Pb-based catalyst needs to be added for reaction, and the reaction formula is as follows:
wherein cat represents a catalyst.
As a specific implementation method of the embodiment of the present invention, as shown in fig. 1, the implementation process is as follows:
reacting the organic waste liquid with a chlorine substituting agent, wherein the chlorine substituting agent is NaOH or KOH, the reaction temperature is 60-200 ℃, the pressure is 0.1-2.0MPa, and the reaction time is 0.5-2 h. The mol ratio of NaOH or KOH to chlorine in the organic waste liquid is 1:1-1:1.2, so that the organic waste liquid and the chlorine substituting agent are ensured to continuously and uniformly react in the reaction process.
Adjusting the pH value of the organic waste liquid containing inorganic chloride to be neutral, and separating to obtain a water-soluble aqueous phase solution and a water-insoluble organic phase solution;
desalting the water phase solution, and separating to obtain inorganic chloride concentrated solution and dechlorination solution;
the dechlorination solution and the organic phase solution enter into the reactor to be degraded through oxidation reaction, wherein the oxidation reaction is incineration oxidation reaction, supercritical oxidation reaction or wet oxidation reaction. The oxidant for the oxidation reaction is oxygen-enriched air or liquid oxygen.
Evaporating the inorganic chloride salt concentrated solution to obtain a crystallization mother solution, settling the crystallization mother solution, and dehydrating the crystallization salt concentrated solution obtained by settling to obtain solid salt.
The method for treating the chlorinated organic matter-containing waste liquid has the beneficial effects that: compared with the prior art, the method for treating the chlorinated organic matter-containing waste liquid comprises the steps of firstly converting organic chlorine in the organic matter waste liquid into inorganic chloride by using a chlorine substitute, adjusting the pH value of the organic matter waste liquid containing the inorganic chloride to be neutral, separating a water-soluble aqueous phase solution from a water-insoluble organic phase solution, and performing dechlorination and separation on the aqueous phase solution to obtain an inorganic chloride concentrated solution and a dechlorination solution, wherein the inorganic chloride concentrated solution can be used for extracting the inorganic chloride, and the dechlorination solution and the organic phase solution are subjected to oxidation reaction degradation. The chlorine element is the main reason for forming dioxin and hydrogen chloride in the treatment process, the invention firstly carries out chlorine substitution reaction on the organic waste liquid, then adjusts the organic waste liquid containing inorganic chloride to be neutral, so that the aqueous phase solution is separated from the organic phase solution, the chlorine element is dissolved in the aqueous phase solution, the organic phase solution is directly oxidized and reversely degraded, and the aqueous phase solution is firstly dechlorinated and then is subjected to oxidation reaction degradation treatment, thereby avoiding forming dioxin and hydrogen chloride in the treatment process, corroding equipment and polluting the environment, and simultaneously, the inorganic chloride concentrated solution can be reused, and resource waste is avoided.
In this example, if the pH of the organic waste liquid containing inorganic chloride is adjusted to be neutral, and then the organic waste liquid containing inorganic chloride is completely dissolved in water, it indicates that all separated organic waste liquid is an aqueous phase solution and the content of the organic phase solution is zero. In this embodiment, a process of performing a chlorine substitution reaction on an organic waste liquid, adjusting the organic waste liquid containing an inorganic chloride salt to a neutral state to obtain an aqueous phase solution, and dechlorinating the aqueous phase solution is referred to as a pre-dechlorination treatment.
As a specific implementation method of the embodiment of the present invention, as shown in fig. 1, the implementation process is as follows:
reacting the organic waste liquid with a chlorine substituting agent which is H2With NaOH or H2With KOH, H2Used in combination with a Ni-based catalyst or a Pb-based catalyst. The reaction temperature is 60-200 ℃, the pressure is 0.1-2.0MPa, and the reaction time is 0.5-2 h. Wherein H2The mol ratio of the NaOH or KOH to the chlorine in the organic waste liquid is 2:1-2.2:1, and the mol ratio of the NaOH or KOH to the chlorine in the organic waste liquid is 1:1-1:1.2, so that the reaction is ensuredIn the reaction process, the organic waste liquid and the chlorine substituting agent continuously and uniformly react.
When H is present2When the catalyst is matched with a Ni-based catalyst for use, the molar ratio of Ni in the Ni-based catalyst to chlorine in the organic waste liquid is 1:45-1: 90;
when H is present2When the catalyst is matched with a Pb-based catalyst for use, the molar ratio of Pb in the Pb-based catalyst to chlorine in organic waste liquid is 1: 500-1: 800.
adjusting the pH value of the organic waste liquid containing inorganic chloride to be neutral, and separating to obtain a water-soluble aqueous phase solution and a water-insoluble organic phase solution;
desalting the water phase solution, and separating to obtain inorganic chloride concentrated solution and dechlorination solution;
the dechlorination solution and the organic phase solution enter into an oxidation reaction for degradation, wherein the oxidation reaction is an incineration oxidation reaction, a supercritical oxidation reaction or a wet oxidation reaction. The oxidant for the oxidation reaction is oxygen-enriched air or liquid oxygen.
Evaporating the inorganic chloride salt concentrated solution to obtain a crystallization mother solution, settling the crystallization mother solution, and dehydrating the crystallization salt concentrated solution obtained by settling to obtain solid salt.
In the embodiment, the mole ratio of the chlorine element to the chlorine substituting agent and the catalyst in the organic waste liquid is set, so that the organic waste liquid and the chlorine substituting agent react more fully, the substitution rate is improved, and the waste is avoided.
The method comprises the steps of reacting the organic waste liquid with a chlorine substituting agent in a converter, converting chlorine in chlorinated organic substances into chloride to generate organic waste liquid containing inorganic chloride, adjusting the pH value of the organic waste liquid containing the inorganic chloride to be neutral, and then separating to obtain an aqueous phase solution for subsequent desalination treatment. The aqueous phase solution is desalted by a desalter. The desalting device is provided with a cation exchange membrane and an anion exchange membrane, and a channel is arranged between the cation exchange membrane and the anion exchange membrane. Cation exchange membranes allow only cations to permeate and reject blocking anions, and anion exchange membranes allow only anions to permeate and reject blocking cations. The regulating current is formed by applying regulating voltage to the aqueous phase solution, the aqueous phase solution is under the action of the regulating current, when the aqueous phase solution flows through a channel between the anion exchange membrane and the cation exchange membrane, anions move towards the anode direction, and cations move towards the cathode direction.
During dechlorination, the adjusting voltage is adjusted to ensure the dechlorination efficiency and dechlorination rate. When the aqueous solution enters the channel, the regulating voltage is gradually increased, and the regulating current is increased along with the increase of the regulating voltage, so that the flow efficiency of ions in the aqueous solution is improved; when the regulating voltage is continuously increased and the regulating current is slowly increased, stopping increasing the regulating voltage and keeping the regulating voltage stable; after the regulated voltage is kept stable for a period of time, when the regulated current begins to decrease, the regulated voltage is gradually decreased along with the decrease of the regulated current, so that the desalting treatment is completed. When the regulated current begins to decrease, the content of inorganic salt ions in the aqueous solution is reduced, and if the regulated voltage is still kept high, the resource waste is caused.
In the embodiment, the desalination device is low in organic matter impurity content in the inorganic chloride concentrated solution obtained by arranging the anion exchange membrane, the cation exchange membrane and externally applying the regulating voltage, so that the purity of the subsequent obtained solid salt is ensured, the efficiency of dechlorination treatment is improved by regulating the regulating voltage, and resource waste is avoided.
As a specific implementation method of the embodiment of the invention, the concentrated solution of the inorganic chloride salt is passed through an evaporator to obtain a crystallization mother liquor, and the crystallization mother liquor is passed through a salt separation device to obtain solid salt. The salt separating device comprises a thickener and a centrifuge, the crystallization mother liquor obtained by evaporation is settled in the thickener, the supernatant overflows from the periphery of the top of the thickener, and returns to the evaporator to continue to evaporate and crystallize. And (4) sending the concentrated liquid of the crystallized salt obtained by sedimentation of the thickener to a centrifuge from the thickener, and performing centrifugal dehydration to obtain solid salt.
Example 1
The COD of the waste liquid produced by epoxy resin enterprises is 30 ten thousand mg/L, and the chlorine content is 3 ten thousand mg/L.
The chlorine substituting agent is sodium hydroxide alkali liquor, the concentration of the sodium hydroxide alkali liquor is about 3.7%, and the molar ratio of NaOH to chlorine in the organic waste liquid is 1: 1.1, the reaction temperature is 100 ℃, the pressure is 0.1MPa, the reaction time is 0.5h, and the reaction process ensures that the organic waste liquid and the chlorine substituent are continuously and uniformly mixed and reacted;
adjusting the pH of the organic waste liquid containing sodium chloride salt to be neutral by concentrated hydrochloric acid, separating to obtain an aqueous phase solution and an organic phase solution, desalting the aqueous phase solution by a dechlorination device, and separating to obtain a sodium chloride salt concentrated solution and a dechlorination solution;
the dechlorination solution and the organic phase solution are degraded through supercritical oxidation reaction at the temperature of 600 ℃ and the pressure of 23 MPa; and (3) evaporating and crystallizing the sodium chloride concentrated solution through an evaporator, settling the sodium chloride concentrated solution through a thickener, and centrifugally dewatering the sodium chloride concentrated solution through a centrifugal pump to obtain solid sodium chloride.
Through detection, the conversion rate of converting organic chlorine into sodium chloride is 99%, the removal rate of sodium chloride of a separation membrane for desalination is 95%, and COD of a sodium chloride concentrated solution is 100 mg/L. The chlorine concentration of the dechlorination liquid finally obtained by the pretreatment dechlorination is 2000mg/L, and the total chlorine removal rate is 94 percent. The sodium chloride salt concentrated solution is evaporated, crystallized, settled and centrifugally dehydrated to obtain 51.4kg/t of sodium chloride salt with the purity of 99.9 percent. COD of system effluent obtained by oxidizing and degrading the organic phase solution and the dechlorination solution by supercritical water is 25mg/L, the requirement of local sewage plant connection is met, and the generated tail gas meets the local tail gas emission standard.
Example 2
The COD of the production waste liquid of the pesticide enterprises is 45 ten thousand mg/L, and the chlorine content is 5 ten thousand mg/L.
The chlorine substituting agent is sodium hydroxide alkali liquor and H2And the Ni-based catalyst is matched, the concentration of the sodium hydroxide alkali liquor is about 5.6 percent, and the molar ratio of NaOH to chlorine in the organic waste liquid is 1:1, H2The mol ratio of the chlorine in the organic waste liquid to the chlorine in the organic waste liquid is 2:1, molar ratio of Ni in Ni-based catalyst to chlorine in organic waste liquidThe reaction temperature is 60 ℃, the pressure is 0.4MPa, the reaction time is 1h, and the continuous and uniform mixing reaction of the organic waste liquid and the chlorine substituting agent is ensured in the reaction process;
adjusting the pH of the organic waste liquid containing sodium chloride salt to be neutral by concentrated hydrochloric acid, separating to obtain an aqueous phase solution and an organic phase solution, desalting the aqueous phase solution by a desalting device, and separating to obtain a sodium chloride salt concentrated solution and a dechlorination solution;
the organic phase solution and dechlorination solution are degraded through incineration oxidation reaction, and the oxidation reaction temperature is 1100 ℃; and (3) evaporating and crystallizing the sodium chloride concentrated solution through an evaporator, settling the sodium chloride concentrated solution through a thickener, and centrifugally dewatering the sodium chloride concentrated solution through a centrifugal pump to obtain solid sodium chloride.
Through detection, the conversion rate of converting organic chlorine into sodium chloride is 97%, the removal rate of sodium chloride of a separation membrane for desalination is 93%, and COD of a sodium chloride concentrated solution is 150 mg/L. The chlorine concentration of the dechlorination liquid finally obtained by the pretreatment dechlorination is 5000mg/L, and the total chlorine removal rate is 90 percent. The sodium chloride salt concentrated solution is evaporated, crystallized, settled and centrifugally dehydrated to obtain 76.2kg/t of solid salt with the purity of 99.9 percent. COD of system effluent obtained by incinerating, oxidizing and degrading the organic phase solution and the dechlorinating solution is 45mg/L, the requirement of local sewage plant for pipe connection is met, and the generated tail gas meets the control standard of hazardous waste incineration pollutants.
Example 3
The COD of the production waste liquid of the pharmaceutical enterprise is 20 ten thousand mg/L, and the chlorine content is 4 ten thousand mg/L.
The chlorine substituting agent is potassium hydroxide alkali liquor, the concentration of the potassium hydroxide alkali liquor is about 7.6%, and the molar ratio of KOH to chlorine in the organic waste liquid is 1:1.2, the reaction temperature is 200 ℃, the pressure is 2MPa, the reaction time is 2h, and the reaction process ensures that the organic waste liquid and the chlorine substituting agent are continuously and uniformly mixed and reacted;
adjusting the pH of the organic waste liquid containing potassium chloride salt to be neutral by concentrated hydrochloric acid, separating to obtain an aqueous phase solution and an organic phase solution, desalting the aqueous phase solution by a desalting device, and separating to obtain a potassium chloride salt concentrated solution and a dechlorination solution;
degrading the organic phase solution and the dechlorination solution through wet oxidation reaction at the temperature of 300 ℃ and under the pressure of 16 MPa; and (3) evaporating and crystallizing the potassium chloride concentrated solution through an evaporator, settling the potassium chloride concentrated solution through a thickener, and centrifugally dewatering the potassium chloride concentrated solution through a centrifugal pump to obtain solid potassium chloride.
Through detection, the conversion rate of converting organic chlorine into potassium chloride is 98%, the removal rate of potassium chloride salt of a separation membrane for desalting treatment is 92%, and the COD of a potassium chloride salt concentrated solution is 120 mg/L. The chlorine concentration of dechlorination liquid obtained by the pretreatment and the dechlorination is 3000mg/L, and the total chlorine removal rate is 90 percent. The potassium chloride salt concentrated solution is evaporated, crystallized, settled and centrifugally dewatered to obtain 93.0kg/t of potassium chloride salt with the purity of 99.9 percent. COD of system effluent obtained by degrading the organic phase solution and the dechlorination solution through wet oxidation reaction is 100mg/L, the requirement of local sewage plant connection is met, and the generated tail gas meets the control standard of hazardous waste incineration pollutants.
Example 4
The COD of the waste liquid of a certain chemical production is 50 ten thousand mg/L, and the chlorine content is 6 ten thousand mg/L.
The chlorine substituting agent is potassium hydroxide alkali liquor and H2And the Pb-based catalyst is matched, the concentration of potassium hydroxide alkali liquor is about 11.4%, and the molar ratio of KOH to chlorine in the organic waste liquid is 1:1.2, H2The mol ratio of the chlorine in the organic waste liquid to the chlorine in the organic waste liquid is 2.2:1, the molar ratio of Pb in the Pb-based catalyst to chlorine in the organic waste liquid is 1:500, the reaction temperature is 80 ℃, the pressure is 0.5MPa, the reaction time is 1.5h, and the continuous and uniform mixing reaction of the organic waste liquid and the chlorine substituting agent is ensured in the reaction process;
adjusting the pH of the organic waste liquid containing potassium chloride salt to be neutral by concentrated hydrochloric acid to obtain all aqueous phase solutions, wherein the content of the organic phase solution is zero, desalting the aqueous phase solutions by a desalting device, and separating to obtain a potassium chloride salt concentrated solution and a dechlorination solution;
the dechlorination solution is degraded through supercritical oxidation reaction, the temperature of the oxidation reaction is 650 ℃, and the pressure is 22.5 MPa; and (3) evaporating and crystallizing the potassium chloride concentrated solution through an evaporator, settling the potassium chloride concentrated solution through a thickener, and centrifugally dewatering the potassium chloride concentrated solution through a centrifugal pump to obtain solid potassium chloride.
Through detection, the conversion rate of converting organic chlorine into potassium chloride is 99.9%, the removal rate of potassium chloride of a separation membrane subjected to desalination treatment is 96%, and the COD of a potassium chloride concentrated solution is 200 mg/L. The chlorine concentration of the dechlorination liquid finally obtained by the pretreatment dechlorination is 2400mg/L, and the total chlorine removal rate is 96 percent. The potassium chloride salt concentrated solution is evaporated, crystallized, settled and centrifugally dewatered to obtain 145.6kg/t of potassium chloride salt with the purity of 99.9 percent. COD of system effluent obtained by degrading dechlorination liquid through supercritical oxidation reaction is 50mg/L, the requirement of local sewage plant connection is met, and the generated tail gas meets the local tail gas discharge standard.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The method for treating the chlorinated organic matter-containing waste liquid is characterized by comprising the following steps of:
reacting the organic waste liquid with a chlorine substituting agent, and converting organic chlorine in the organic waste liquid into inorganic chloride;
adjusting the pH value of the organic waste liquid containing inorganic chloride to be neutral, and separating to obtain a water-soluble aqueous phase solution and a water-insoluble organic phase solution;
desalting the water-phase solution, and separating to obtain an inorganic chloride concentrated solution and a dechlorination solution;
and degrading the organic phase solution and dechlorination liquid through oxidation reaction.
2. The method according to claim 1, wherein the chlorine-substituting agent is NaOH, KOH or H2With NaOH or H2With KOH, said H2Used in combination with a Ni-based catalyst or a Pb-based catalyst.
3. The method for treating the chlorinated organic matter-containing waste liquid as claimed in claim 2, wherein the reaction temperature of the reaction between the organic matter waste liquid and the chlorine substitute is controlled to be 60-200 ℃, the pressure is controlled to be 0.1-2.0Mpa, and the reaction time is 0.5-2 hours.
4. The method for treating the chlorinated organic matter-containing waste liquid as claimed in claim 2, wherein the molar ratio of NaOH or KOH to chlorine in the organic matter-containing waste liquid is 1:1 to 1: 1.2.
5. The method according to claim 4, wherein the H is hydrogen2The mol ratio of the Ni in the Ni-based catalyst to the chlorine in the organic waste liquid is 2:1-2.2:1, the mol ratio of the Ni in the Ni-based catalyst to the chlorine in the organic waste liquid is 1:45-1:90, and the mol ratio of the Pb in the Pb-based catalyst to the chlorine in the organic waste liquid is 1: 500-1: 800.
6. the method according to claim 1, wherein the aqueous solution is desalted by passing through a separation membrane, and the concentrated solution of inorganic chloride salt is passed through the separation membrane.
7. The method according to claim 6, wherein the separation membrane comprises a cation exchange membrane and an anion exchange membrane, a channel is provided between the anion exchange membrane and the cation exchange membrane, and ions in the aqueous solution move toward the anion exchange membrane or the cation exchange membrane under the action of the control voltage.
8. The method according to claim 7, wherein the voltage regulation process comprises the steps of:
gradually increasing the regulating voltage, wherein the regulating current is increased along with the increase of the regulating voltage;
when the adjusting voltage is continuously increased and the adjusting current increases slowly, stopping increasing the adjusting voltage and keeping the adjusting voltage stable;
when the regulating current begins to decrease, the regulating voltage is gradually decreased along with the decrease of the regulating current.
9. The method according to claim 1, wherein the oxidation reaction is an incineration oxidation reaction, a supercritical oxidation reaction, or a wet oxidation reaction.
10. The method for treating a chlorinated organic matter-containing waste liquid according to claim 1, wherein the concentrated solution of inorganic chloride salt is subjected to evaporation crystallization to obtain a crystallization mother liquid, the crystallization mother liquid is subjected to sedimentation treatment, and the concentrated solution of crystallization salt obtained by the sedimentation treatment is dehydrated to obtain solid salt.
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| CN114278949A (en) * | 2021-12-07 | 2022-04-05 | 北京航化节能环保技术有限公司 | Incineration system and incineration process for treating fluorine-containing chlorine-containing salt-containing waste liquid |
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| CN109851113A (en) * | 2019-01-02 | 2019-06-07 | 广东益诺欧环保股份有限公司 | A kind of method and system for the organic chloride wastewater of high concentration of degrading |
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