CN117361731A - Method for treating chlorine-containing organic wastewater by supercritical water oxidation - Google Patents
Method for treating chlorine-containing organic wastewater by supercritical water oxidation Download PDFInfo
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- CN117361731A CN117361731A CN202311268834.6A CN202311268834A CN117361731A CN 117361731 A CN117361731 A CN 117361731A CN 202311268834 A CN202311268834 A CN 202311268834A CN 117361731 A CN117361731 A CN 117361731A
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- 239000000460 chlorine Substances 0.000 title claims abstract description 102
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 95
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000009284 supercritical water oxidation Methods 0.000 title claims abstract description 30
- 239000002351 wastewater Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 239000010815 organic waste Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 229910001504 inorganic chloride Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 70
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 51
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 39
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 25
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000008247 solid mixture Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000006911 nucleation Effects 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 206010035148 Plague Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- 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
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- 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
- C02F2101/363—PCB's; PCP's
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/14—Maintenance of water treatment installations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention relates to a method for treating chlorine-containing organic wastewater by supercritical water oxidation, which is characterized by comprising the following steps: step one, for chlorine concentration higher than 10mg/L, containing two kinds of inorganic chloride MCl and organic chlorine, wherein M is the treatment of chlorine-containing organic waste liquid of metal ions, firstly, pretreating the chlorine-containing organic waste liquid to a condition that supercritical water oxidation equipment can be fed; specifically, if the COD of the chlorine-containing organic waste liquid is higher than 15 ten thousand mg/L, the chlorine-containing organic waste liquid needs to be diluted to 10-15 ten thousand ppm; if the COD is lower than 5 ten thousand COD, adding an organic auxiliary agent to improve the COD to 10 ten thousand to 15 ten thousand COD; the chlorine-containing substances are discharged in time, so that the time of existence of Cl in supercritical equipment is reduced, the probability of equipment corrosion is reduced, and particularly, the high-temperature and oxygen-containing reaction kettle is protected.
Description
Technical Field
The invention belongs to the technical fields of energy, chemical industry and environmental protection, relates to a process for treating chlorine-containing wastewater by supercritical water oxidation, and in particular relates to a chlorine removal process in supercritical water oxidation technology for treating high-chlorine-containing organic waste liquid. The method is also suitable for removing chloride ions in subcritical water.
Background
Supercritical water oxidation (SCWO) is carried out by using water under supercritical state (pressure of more than 22.1MPa and temperature of more than 374.3deg.C) in oxidizing agent (such as oxygen,Air or hydrogen peroxide, etc.), and through the free radical reaction at high temperature and high pressure, the organic matters are oxidized and decomposed into CO 2 、H 2 O、N 2 And other harmless micromolecular substances, so that the method for decomposing and removing the organic matters has the organic pollutant removal rate of more than 99 percent, and the inorganic salt has extremely low solubility in supercritical water and is easy to separate; is a novel organic wastewater treatment technology with high purification efficiency, fast reaction rate, thorough decomposition and no secondary pollution. SCWO is a very promising technology, and SCWO is listed as the most promising waste treatment technology in "energy and environment" which is one of the six fields listed as the key technology in the united states.
Although the supercritical water oxidation technology has obvious advantages, two major problems which plague the industrialized popularization of the supercritical water oxidation technology, namely corrosion and salt deposition blockage, exist. Most of the existing commercial or pilot plant treatment objects are organic wastewater with low salt content and low chloride ion content. The chloride ion has the characteristics of small ionic radius, strong penetrating power and strong adsorption by the metal surface. The higher the concentration of chloride ions, the stronger the conductivity of the aqueous solution, the lower the resistance of the electrolyte, the easier the chloride ions reach the metal surface, and the progress of local corrosion is accelerated; the existence of chloride ions in an acidic environment can form a chloride salt layer on the surface of metal and replace FeCO with protective performance 3 Films, resulting in high pitting rates. During the etching process, chloride ions are not only enriched in pit but also in the areas where pit is not generated, which are the early stages of pit formation. Currently, limited thereto, most cannot be removed by supercritical water oxidation technology equipment for chlorine-containing wastewater.
Disclosure of Invention
The invention provides a method for treating chlorine-containing organic waste liquid by supercritical water oxidation technology, which solves the problem that the existing supercritical water oxidation technology cannot treat the chlorine-containing organic waste liquid.
The method for treating the chlorine-containing organic wastewater by supercritical water oxidation is characterized by comprising the following steps of:
step one, for chlorine concentration higher than 10mg/L, containing two kinds of inorganic chloride MCl and organic chlorine, wherein M is the treatment of chlorine-containing organic waste liquid of metal ions, firstly, pretreating the chlorine-containing organic waste liquid to a condition that supercritical water oxidation equipment can be fed; specifically, if the COD of the chlorine-containing organic waste liquid is higher than 15 ten thousand mg/L, the chlorine-containing organic waste liquid needs to be diluted to 10-15 ten thousand ppm; if the COD is lower than 5 ten thousand COD, adding an organic auxiliary agent to improve the COD to 10 ten thousand to 15 ten thousand COD;
step two, pumping the pretreated chlorine-containing organic waste liquid in the step one into a preheater I of a supercritical water oxidation system through a high-pressure pump, and heating the chlorine-containing organic waste liquid to 150-200 ℃ in the preheater I; then the chlorine-containing organic waste liquid enters a preheater II, and the chlorine-containing organic waste liquid is heated to 250-300 ℃ in the preheater II; at this point, the supercritical water state is approached;
step three, inorganic chlorine in the organic waste liquid containing chlorine in the preheater II forms an MCl-MOH solid mixture with ionized OH-crystal nucleation in supercritical water, wherein M is a metal ion; MOH is fixed in amorphous MCl clusters, the solubility of MCl.MOH in near critical water is reduced, and precipitation is formed along with the growth of crystallization and enters a salt discharging device at the lower end of a preheater II; ionized H+ and Cl-in supercritical water form HCl association and are separated to enter a near-critical water state, the HCl association enters the upper part of a preheater II, a chlorine discharge valve at the top end of the preheater II is opened, high-concentration water containing HCl enters a cooler along with the supercritical water to be cooled, and then is discharged from a reactor water purifying port, and the HCl association enters a water outlet back pressure valve to be in a normal state; the MCl-MOH solid mixture is deposited downwards due to gravity, a salt discharging device falling into the lower part of the reactor is not heated and kept warm, the solubility of salt is increased due to the fact that the temperature is reduced to be in a non-supercritical water state, crystallized MCl-MOH is dissolved again or partially dissolved, and after a set time, a salt discharging valve II of the preheater is opened to discharge the MCl-MOH solid mixture;
step four, after chlorine removal through a preheater II, the waste liquid containing the organic chlorine enters a reaction kettle to be heated to 360-650 ℃, and is in a supercritical water state at the moment;
reacting organic chlorine in the chlorine-containing organic waste liquid in the reaction kettle with oxygen pumped by a high-pressure oxygen pump to generate Cl ions, and crystallizing and nucleating in supercritical water to form an MCl-MOH solid mixture, wherein M is a metal ion; MOH is fixed in the amorphous MCl cluster, and forms sediment along with the growth of crystallization to enter a salt collecting device at the lower end of the reaction kettle; HCl association is separated to enter supercritical water state and is positioned at the upper part of the reaction kettle; the chlorine discharge valve at the top end of the reaction kettle is opened, HCl-containing high-concentration water enters the cooler along with supercritical water to be cooled and then is discharged from the purification water port of the reactor, and the HCl-containing high-concentration water flows out normally after passing through the back pressure valve of the water outlet pipe; after the set time, opening a salt discharging valve of the reaction kettle to discharge the MCl.MOH solid mixture;
step six, cooling hydrogen chloride discharged from a chlorine discharge port at the top end of the preheater II and the reaction kettle by a cooler, separating by a gas-liquid separator after passing through a pressure reducing valve, wherein the discharged materials are HCl gas and hydrochloric acid, and the HCl gas is collected by a balloon;
step seven, organic waste liquid is subjected to supercritical water oxidation treatment and then sequentially returns to the preheater II and the preheater I through a tube pass to perform heat exchange; and cooling by a cooler, flowing out by a back pressure valve, and finally discharging by a gas-liquid separator.
The organic auxiliary agent in the first step is methanol and sucrose solution organic solvent.
If the chlorine-containing organic waste liquid contains solid particles, the solid particles need to be filtered through a vibrating screen.
And step six, when the output of HCl gas and hydrochloric acid is not high, introducing a gas exhaust port into the NaOH solution to neutralize and generate NaCl solution.
Compared with the prior art, the invention has the advantages that:
the invention utilizes the fact that the solubility of inorganic substances such as MCl and the like in supercritical water can be rapidly reduced along with the rising of temperature and pressure, and ions ionized in normal state tend to form ions in the supercritical water to deposit crystals. CL ions combine with H to form HCl, above the supercritical (near) water. The chlorine-containing substances are discharged in time, so that the time of existence of Cl in supercritical equipment is reduced, the probability of equipment corrosion is reduced, and particularly, the high-temperature and oxygen-containing reaction kettle is protected.
In supercritical (near) water, MCl solubility decreases rapidly with increasing temperature, i.e. its equilibrium concentration ceq decreases rapidly. Both the absolute supersaturation deltac and the supersaturation coefficient s of the NaCl supercritical water system increase rapidly as ceq decreases. At extremely high supersaturation in supercritical water, MCl instantaneously forms a large number of clusters and nanoparticles to become crystal nuclei and grow. The initially formed MCl clusters and nanoparticles can be regarded as amorphous NaCl hydrate in the course of nucleation of these particles, water molecules being adsorbed to the periphery of MCl nuclei clusters and occupying the interstices of these MCl clusters, being trapped and enclosed inside MCl nuclei clusters during MCl nanocrystal growth. The electrostatic field generated by NaCl crystallization and condensation ions is up to 1010V/m, and can drive the decomposition of pressure-bearing water molecules, and the decomposition equation is as follows:
mMCl(s)+nH2O(sc)→MCl(sc)+MOH·(m－1)MCl(s)+(n－1)H 2 O(sc)
compared with other inventions, the invention provides a method for treating chlorine-containing organic wastewater by a supercritical water oxidation method. For the inorganic chlorine in the wastewater, the inorganic chlorine can be discharged from the top end in the form of HCl in advance and discharged from the bottom end in the form of deposited salt of MCl.MOH type solid mixture in advance. For Cl in the organic state (like polychlorinated biphenyl, abbreviated as PCB), HCl generated after reaction with oxygen is discharged at the top of the reaction vessel, and mcl.moh type solid mixture is discharged from the bottom in the form of deposited salt. The chlorine-containing substances are discharged in time, so that the time of existence of Cl in supercritical equipment is reduced, the probability of equipment corrosion is reduced, and particularly, the high-temperature and oxygen-containing reaction kettle is protected.
Drawings
FIG. 1 is a process flow diagram of treating chlorine-containing wastewater by supercritical water oxidation reaction.
The method comprises the steps of (1) enabling chlorine-containing wastewater to enter a shell pass of a preheater I, (2) enabling chlorine-containing wastewater to enter a shell pass of a preheater II from the bottom end, (3) enabling chlorine-containing wastewater to enter the top of a reaction kettle, (4) enabling chlorine-containing wastewater to enter a tube pass of the preheater II after the chlorine-containing wastewater is reacted with oxygen completely, (5) enabling chlorine-containing wastewater to enter a tube pass of the preheater I, (6) enabling chlorine-containing wastewater to enter a cooler I, and (7) enabling chlorine-containing wastewater to enter a gas-water separator I through a back pressure valve I1, wherein gas containing CO2, N2, water vapor and the like is discharged into the atmosphere; the liquid is clean water after treatment, COD is less than 100ppm, and the liquid is discharged into a collecting device.
The route (8) is an oxygen input route, and enters a reaction kettle to react with the organic waste liquid; in particular, in order to ensure the full oxidation of the organic waste liquid, the oxygen is generally in excess of 50% -100%.
The route (9) is a chlorine discharge route of the organic waste liquid in the preheater II, and the organic waste liquid is cooled by the cooler II and then passes through the routeThrough the back pressure valve II 2, the gas enters the gas-liquid separator II, and the gas phase is HCl gas and is collected by a balloon. If the yield is not large, the gas removal port can be vented to NaOH solution to neutralize to produce NaCl solution.
Route r is the route through which the organic chlorine is cooled from cooler II after reactionEnters a back pressure valve 3 and then enters a gas-liquid separator II, and the gas phase is HCl gas and is collected by a balloon. If the yield is not large, the gas removal port can be vented to NaOH solution to neutralize to produce NaCl solution.
The salt solution of the salt discharging port at the bottom of the preheater II and the reaction kettle is cooled by the cooler II and the cooler I after the MCl MOH solid mixture flows out and passes through the path->And the gas enters a back pressure valve IV 4 and then enters a gas-liquid separator III.
Wherein, 1 is a back pressure valve I, 2 is a back pressure valve II, 3 is a back pressure valve III, and 4 is a back pressure valve IV.
Detailed Description
The invention comprises the following steps:
step one, pretreating chlorine-containing organic waste liquid to a condition that supercritical water oxidation equipment can be fed; specifically, if the COD of the chlorine-containing organic waste liquid is higher than 15 ten thousand mg/Lppm, the chlorine-containing organic waste liquid needs to be diluted to 10-15 ten thousand ppm; if the COD is lower than 5 ten thousand COD, adding an organic auxiliary agent to improve the COD to 10 ten thousand to 15 ten thousand COD; the chlorine concentration is higher than 10mg/L, and the chlorine-free catalyst comprises two inorganic chlorides MCl (M is a metal ion) and organic chlorine.
Step two, pumping the pretreated chlorine-containing organic waste liquid in the step one into a preheater I of a supercritical water oxidation system through a high-pressure pump, and heating the chlorine-containing organic waste liquid to 150-200 ℃ in the preheater I; then the chlorine-containing organic waste liquid enters a preheater II, and the chlorine-containing organic waste liquid is heated to 250-300 ℃ in the preheater II; at this point, the supercritical water state is approached;
step three, inorganic chloride ions in the organic waste liquid containing chlorine in the preheater II are nucleated with ionized OH-crystals in supercritical water to form an MCl-MOH solid mixture, wherein M is a metal ion; MOH is fixed in amorphous MCl clusters, the solubility of MCl.MOH in near critical water is reduced, and as crystallization grows up, sediment is formed and enters a salt collecting and discharging device at the lower end of the preheater II; h+ ionized in supercritical water and Cl-form HCl association, and then the HCl association is separated to enter a supercritical water state, and the HCl association is positioned at the upper part of a preheater II; the chlorine discharge valve at the top end of the preheater II is opened, HCl-containing high-concentration water enters the cooler along with supercritical water to be cooled, and then is discharged from the reactor purification water gap, and the HCl-containing high-concentration water becomes a normal state after passing through the back pressure valve of the water outlet pipe; the MCl-MOH solid mixture is deposited downwards due to gravity, a salt discharging device is arranged in a subcritical region at the lower part of the reactor, the salt discharging device is not heated and is kept warm, and then the temperature is reduced to be in a non-supercritical water state, so that the solubility of salt is increased, crystallized MCl-MOHNaCl and NaOH are dissolved or partially dissolved again, and the pH value of the discharged salt water is increased; after the set time, opening a salt discharging valve II of the preheater to discharge the MCl.MOH solid mixture;
and fourthly, after chlorine removal through the preheater II, the waste liquid containing the organic chlorine enters a reaction kettle to be heated to 360-650 ℃, and is in a supercritical water state at the moment.
Reacting organic chlorine in the chlorine-containing organic waste liquid in the reaction kettle with oxygen pumped by a high-pressure oxygen pump to generate Cl ions, and crystallizing and nucleating in supercritical water to form an MCl-MOH solid mixture, wherein M is a metal ion; MOH is fixed in the amorphous MCl cluster, and forms sediment along with the growth of crystallization to enter a salt collecting device at the lower end of the reaction kettle; HCl association is separated to enter supercritical water state and is positioned at the upper part of the reaction kettle; the chlorine discharge valve at the top end of the reaction kettle is opened, HCl-containing high-concentration water enters the cooler along with supercritical water to be cooled and then is discharged from the purification water port of the reactor, and the HCl-containing high-concentration water flows out normally after passing through the back pressure valve of the water outlet pipe; after the set time, opening a salt discharging valve of the reaction kettle to discharge the MCl.MOH solid mixture;
step six, cooling hydrogen chloride discharged from a chlorine discharge port at the top end of the preheater II and the reaction kettle by a cooler, separating by a gas-liquid separator after passing through a pressure reducing valve, wherein the discharged materials are HCl gas and hydrochloric acid, and the HCl gas is collected by a balloon;
and step seven, sequentially returning the organic waste liquid to the preheater II and the preheater I through a tube pass after supercritical water oxidation treatment, and performing heat exchange. And cooling by a cooler, flowing out by a back pressure valve, and finally discharging by a gas-liquid separator.
Wherein the organic auxiliary agent in the first step is methanol and sucrose solution organic solvent.
If the chlorine-containing organic waste liquid contains solid particles, the solid particles need to be filtered through a vibrating screen.
And step six, when the output of HCl gas and hydrochloric acid is not high, introducing a gas exhaust port into the NaOH solution to neutralize and generate NaCl solution.
Claims (4)
1. The method for treating the chlorine-containing organic wastewater by supercritical water oxidation is characterized by comprising the following steps of:
step one, for chlorine concentration higher than 10mg/L, containing two kinds of inorganic chloride MCl and organic chlorine, wherein M is the treatment of chlorine-containing organic waste liquid of metal ions, firstly, pretreating the chlorine-containing organic waste liquid to a condition that supercritical water oxidation equipment can be fed; specifically, if the COD of the chlorine-containing organic waste liquid is higher than 15 ten thousand mg/L, the chlorine-containing organic waste liquid needs to be diluted to 10-15 ten thousand ppm; if the COD is lower than 5 ten thousand COD, adding an organic auxiliary agent to improve the COD to 10 ten thousand to 15 ten thousand COD;
step two, pumping the pretreated chlorine-containing organic waste liquid in the step one into a preheater I of a supercritical water oxidation system through a high-pressure pump, and heating the chlorine-containing organic waste liquid to 150-200 ℃ in the preheater I; then the chlorine-containing organic waste liquid enters a preheater II, and the chlorine-containing organic waste liquid is heated to 250-300 ℃ in the preheater II; at this point, the supercritical water state is approached;
step three, inorganic chlorine in the organic waste liquid containing chlorine in the preheater II forms an MCl-MOH solid mixture with ionized OH-crystal nucleation in supercritical water, wherein M is a metal ion; MOH is fixed in amorphous MCl clusters, the solubility of MCl.MOH in near critical water is reduced, and precipitation is formed along with the growth of crystallization and enters a salt discharging device at the lower end of a preheater II; ionized H+ and Cl-in supercritical water form HCl association and are separated to enter a near-critical water state, the HCl association enters the upper part of a preheater II, a chlorine discharge valve at the top end of the preheater II is opened, high-concentration water containing HCl enters a cooler along with the supercritical water to be cooled, and then is discharged from a reactor water purifying port, and the HCl association enters a water outlet back pressure valve to be in a normal state; the MCl-MOH solid mixture is deposited downwards due to gravity, a salt discharging device falling into the lower part of the reactor is not heated and kept warm, the solubility of salt is increased due to the fact that the temperature is reduced to be in a non-supercritical water state, crystallized MCl-MOH is dissolved again or partially dissolved, and after a set time, a salt discharging valve II of the preheater is opened to discharge the MCl-MOH solid mixture;
step four, after chlorine removal through a preheater II, the waste liquid containing the organic chlorine enters a reaction kettle to be heated to 360-650 ℃, and is in a supercritical water state at the moment;
reacting organic chlorine in the chlorine-containing organic waste liquid in the reaction kettle with oxygen pumped by a high-pressure oxygen pump to generate Cl ions, and crystallizing and nucleating in supercritical water to form an MCl-MOH solid mixture, wherein M is a metal ion; MOH is fixed in the amorphous MCl cluster, and forms sediment along with the growth of crystallization to enter a salt collecting device at the lower end of the reaction kettle; HCl association is separated to enter supercritical water state and is positioned at the upper part of the reaction kettle; the chlorine discharge valve at the top end of the reaction kettle is opened, HCl-containing high-concentration water enters the cooler along with supercritical water to be cooled and then is discharged from the purification water port of the reactor, and the HCl-containing high-concentration water flows out normally after passing through the back pressure valve of the water outlet pipe; after the set time, opening a salt discharging valve of the reaction kettle to discharge the MCl.MOH solid mixture;
step six, cooling hydrogen chloride discharged from a chlorine discharge port at the top end of the preheater II and the reaction kettle by a cooler, separating by a gas-liquid separator after passing through a pressure reducing valve, wherein the discharged materials are HCl gas and hydrochloric acid, and the HCl gas is collected by a balloon;
step seven, organic waste liquid is subjected to supercritical water oxidation treatment and then sequentially returns to the preheater II and the preheater I through a tube pass to perform heat exchange; and cooling by a cooler, flowing out by a back pressure valve, and finally discharging by a gas-liquid separator.
2. The method for treating chlorine-containing organic wastewater by supercritical water oxidation according to claim 1, wherein the organic auxiliary agent in the step one is methanol or sucrose solution organic solvent.
3. The method for supercritical water oxidation treatment of chlorine-containing organic wastewater according to claim 1 wherein in step one, if the chlorine-containing organic wastewater contains solid particles, the solid particles are filtered through a vibrating screen.
4. The method for treating chlorine-containing organic wastewater by supercritical water oxidation according to claim 1, wherein when the output of the step six is HCl gas and hydrochloric acid is not high, the gas exhaust port is introduced into NaOH solution to neutralize the solution to generate NaCl solution.
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