CN106865860B - Energy recovery type wastewater catalytic wet oxidation treatment device and wastewater treatment method - Google Patents
Energy recovery type wastewater catalytic wet oxidation treatment device and wastewater treatment method Download PDFInfo
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- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 37
- 238000011282 treatment Methods 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 24
- 238000011084 recovery Methods 0.000 title claims abstract description 15
- 238000004065 wastewater treatment Methods 0.000 title claims description 30
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- 238000001704 evaporation Methods 0.000 claims description 14
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- 238000007172 homogeneous catalysis Methods 0.000 claims description 12
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000010948 rhodium Substances 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 4
- 229960001763 zinc sulfate Drugs 0.000 claims description 4
- 238000011221 initial treatment Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 description 18
- 238000007865 diluting Methods 0.000 description 4
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- 239000003643 water by type Substances 0.000 description 3
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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Images
Classifications
-
- 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
- C02F1/048—Purification of waste water by 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- 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
- C02F2303/10—Energy recovery
Abstract
The invention discloses an energy recovery type wastewater catalytic wet oxidation treatment device, wherein a wastewater storage tank and a catalyst storage tank are simultaneously communicated with a first heat exchanger, the first heat exchanger is communicated with a first reaction tower, the first reaction tower is communicated with a second heat exchanger, the second heat exchanger is communicated with a second reaction tower, a heat exchange water outlet of the second heat exchanger is connected with a turbine generator, the second reaction tower is communicated with a first gas-liquid separator, a gas phase outlet of the first gas-liquid separator is communicated with a first tail gas absorption tower, a liquid phase outlet of the first gas-liquid separator is communicated with an MVR evaporator, the MVR evaporator is communicated with a third heat exchanger, the third heat exchanger is communicated with a third reaction tower, the third reaction tower is communicated with a second gas-liquid separator, and a gas phase outlet of the second gas-liquid separator is communicated; the air compressor is used for providing reaction air for the first reaction tower, the second reaction tower and the third reaction tower. The invention has the advantages that: can directly treat high-concentration high-salt-content wastewater, is environment-friendly, has low cost, good effect and small occupied area, and can recycle energy.
Description
Technical Field
The invention relates to the technical field of industrial organic wastewater treatment, in particular to a device and a method for treating high-concentration high-salt-content industrial organic wastewater.
Background
Water pollution is an important problem which needs to be solved in China at present. The problem of water pollution should be solved firstly, the source of pollution, namely the generation and discharge of sewage, and industrial organic wastewater generated by factories is one of the main sources of water pollution. The pollutant components in the industrial wastewater are complex, the biotoxicity is high, the COD is high, the salinity is high, the color is dark, the taste is heavy, and the treatment is very difficult. The main treatment methods at present are: biological methods, extraction methods, incineration methods, fenton methods, ozone methods, and the like, but these methods have disadvantages in that: (1) the treatment cost is high and the treatment effect is poor; (2) the method can not directly treat the wastewater with COD content more than 10 ten thousand mg/L and high salt content, and before the wastewater with high salt content is treated, the COD content and the salt content of the wastewater with high concentration and high salt content must be diluted and reduced, and the treatment steps are complicated; (3) the occupied area of the applied equipment is large; (4) the secondary pollution to the environment and the waste of a large amount of energy exist in the wastewater treatment process, and the energy-saving and environment-friendly effects are achieved.
Disclosure of Invention
The invention aims to provide an energy recovery type wastewater catalytic wet oxidation treatment device and a wastewater treatment method, which can directly and efficiently treat high-concentration high-salt organic wastewater, have no secondary pollution in the wastewater treatment process and can effectively recycle energy.
In order to achieve the purpose, the invention adopts the following technical scheme: the energy recovery type wastewater catalytic wet oxidation treatment device comprises a wastewater storage tank for storing wastewater, a catalyst storage tank for storing a catalyst and an air compressor, wherein a water outlet of the wastewater storage tank and a discharge port of the catalyst storage tank are simultaneously communicated with a feed port of a first heat exchanger, a discharge port of the first heat exchanger is communicated with an inlet of a first reaction tower, an outlet of the first reaction tower is communicated with a feed port of a second heat exchanger, a discharge port of the second heat exchanger is communicated with an inlet of a second reaction tower, a heat exchange water outlet of the second heat exchanger is connected with a turbine generator, an outlet of the second reaction tower is communicated with an inlet of a first gas-liquid separator through the first heat exchanger, a gas phase outlet of the first gas-liquid separator is communicated with an inlet of a first tail gas absorption tower, and a liquid phase outlet of the first gas-liquid separator is communicated with a feed port of an, a condensed water outlet of the MVR evaporator is communicated with a feed inlet of a third heat exchanger, a discharge hole of the third heat exchanger is communicated with an inlet of a third reaction tower, an outlet of the third reaction tower is communicated with an inlet of a second gas-liquid separator through the third heat exchanger, and a gas phase outlet of the second gas-liquid separator is communicated with an inlet of a second tail gas absorption tower; the air compressor simultaneously provides reaction air for the first reaction tower, the second reaction tower and the third reaction tower through pipelines.
Further, the aforesaid catalytic wet oxidation treatment device of energy recovery type waste water, wherein: the outlet of the second reaction tower is communicated with the shell layer of the first heat exchanger, the cold material and the hot material reversely flow through the first heat exchanger, and the shell layer outlet of the first heat exchanger is communicated with the inlet of the first gas-liquid separator.
Further, the aforesaid catalytic wet oxidation treatment device of energy recovery type waste water, wherein: the outlet of the third reaction tower is communicated with the shell of the third heat exchanger, the cold material and the hot material reversely flow through the third heat exchanger, and the outlet of the shell of the third heat exchanger is communicated with the inlet of the second gas-liquid separator.
Further, the aforesaid catalytic wet oxidation treatment device of energy recovery type waste water, wherein: the liquid phase outlet of the first gas-liquid separator is communicated with the feed inlet of the first buffer tank, and the discharge outlet of the first buffer tank is communicated with the feed inlet of the MVR evaporator.
Further, the aforesaid catalytic wet oxidation treatment device of energy recovery type waste water, wherein: and refluxing the distilled mother liquor of the MVR evaporator to the catalyst storage tank.
A method of wastewater treatment comprising the steps of:
(1) mixing a homogeneous catalyst and wastewater, heating and introducing the mixture into a first reaction tower, and carrying out first homogeneous catalytic wet oxidation reaction on the wastewater mixed with the homogeneous catalyst and reaction air provided by an air compressor in the first reaction tower to generate primary treatment water containing the homogeneous catalyst;
(2) cooling the primary treated water generated in the step (1), introducing the primary treated water into a second reaction tower, and carrying out a second homogeneous catalysis wet oxidation reaction on the primary treated water and reaction air provided by an air compressor in the second reaction tower to generate secondary treated water containing a homogeneous catalyst;
(3) then cooling the second treated water generated in the step (2), and introducing the cooled second treated water into a first gas-liquid separator for gas-liquid separation to generate a gas phase and a liquid phase containing a homogeneous catalyst;
(4) then introducing the liquid phase generated in the step (3) into an MVR evaporator for evaporation to generate colorless crystalline salt, condensed water and a distilled mother liquor containing a homogeneous catalyst;
(5) heating the condensed water generated in the step (4), introducing the heated condensed water into a third reaction tower, and carrying out heterogeneous catalytic wet oxidation reaction on the condensed water, a heterogeneous catalyst in the third reaction tower and reaction air provided by an air compressor in the third reaction tower to generate three pieces of treated water;
(6) and (4) cooling the three treated water generated in the step (5), and introducing the cooled treated water into a second gas-liquid separator for gas-liquid separation to generate a gas phase and a liquid phase meeting the discharge standard.
The homogeneous catalyst is one or more of ferric sulfate, ferric nitrate, copper sulfate, copper nitrate, manganese sulfate, manganese nitrate, cobalt sulfate, cobalt nitrate, zinc sulfate, zinc nitrate, nickel sulfate and nickel nitrate.
The heterogeneous catalyst is a noble metal supported catalyst, the carrier of the heterogeneous catalyst is one or more of activated carbon, titanium dioxide, zirconium dioxide, aluminum oxide, silicon dioxide and molecular sieves, and the active component of the heterogeneous catalyst is one or more of ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum and neodymium.
Further, the above wastewater treatment method, wherein: the reaction conditions of the homogeneous catalysis wet oxidation reaction in the step (1) are as follows: the reaction temperature is 250-300 ℃, the reaction pressure is 4.5-9 MPa, and the liquid hourly space velocity is 0.5-3 h-1Wherein the adding amount of the homogeneous catalyst is 50-500 mg (in terms of metal ion) added to each liter of wastewater.
Further, the above wastewater treatment method, wherein: the reaction conditions of the homogeneous catalysis wet oxidation reaction in the step (2) are as follows: the reaction temperature is 220-290 ℃, the reaction pressure is 2.5-8 MPa, and the liquid hourly space velocity is 0.5-3 h-1Wherein the adding amount of the homogeneous catalyst is 50-500 mg (in terms of metal ion) added to each liter of wastewater.
Further, the above wastewater treatment method, wherein: the evaporation conditions of the MVR evaporator in the step (4) are as follows: the evaporation temperature is 50-100 ℃, and the amount of the mother liquor remained after evaporation is controlled to be 1-10% of the amount of the liquid phase generated in the step (3).
Further, the above wastewater treatment method, wherein: the reaction conditions of the heterogeneous catalytic wet oxidation reaction in the step (5) are as follows: the reaction temperature is 180-280 ℃, the reaction pressure is 2.0-7.5 MPa, and the liquid hourly space velocity is 0.5-3 h-1。
Through the implementation of the technical scheme, the wastewater treatment device has the advantages that: (1) the treatment cost is low, the treatment effect is good, the occupied area is small, and the automation degree is high; (2) the wastewater with COD content over 10 ten thousand mg/L and high salt content can be directly treated without diluting the wastewater; (3) no secondary pollution to the environment exists in the wastewater treatment process; (4) the surplus heat is recovered through the heat exchanger, and the steam generated by the heat exchanger is used for generating electricity by the turbine generator, so that the purpose of energy recovery and utilization is achieved, and environmental benefits and economic benefits are achieved; the wastewater treatment method has the advantages that: the treatment efficiency is good, the COD removal rate is high, the COD removal rate is greater than 95.5%, secondary pollution to the environment does not exist in the wastewater treatment process, wastewater with the COD content of more than 10 ten thousand mg/L and high salt content can be directly treated without diluting the wastewater, the method is particularly superior to treatment of wastewater with volatile organic components, the MVR evaporation mother liquor is recycled to prepare a homogeneous catalyst, the problem of concentrated solution is solved, the aim of recycling is achieved, and precipitated salt is colorless clean salt and can be recycled.
Drawings
Fig. 1 is a schematic diagram of the structural principle of an energy recovery type wastewater catalytic wet oxidation treatment device.
Detailed Description
The invention is further described with reference to the following figures and specific examples.
As shown in fig. 1, the energy recovery type wastewater catalytic wet oxidation treatment device comprises a wastewater storage tank 1 for storing wastewater, a catalyst storage tank 2 for storing a catalyst, and an air compressor 3, wherein a water outlet of the wastewater storage tank 1 is communicated with an inlet of a pipeline mixer 6 through a first pipeline 5 provided with a first diaphragm pump 4, a material outlet of the catalyst storage tank 2 is communicated with an inlet of the pipeline mixer 6 through a second pipeline 7, an outlet of the pipeline mixer 6 is communicated with a material inlet of a first heat exchanger 9, a material outlet of the first heat exchanger 9 is communicated with an inlet of a first reaction tower 10, an outlet at the top of the first reaction tower 10 is communicated with a material inlet of a second heat exchanger 11 through a fourth pipeline 12, a material outlet of the second heat exchanger 11 is communicated with an inlet of a second reaction tower 13, and a heat exchange water outlet of the second heat exchanger 11 is connected with a turbine generator 14, the top outlet of the second reaction tower 13 is communicated with the heat exchange water inlet of the first heat exchanger 9 through a fifth pipeline 15, and the heat exchange water outlet of the first heat exchanger 9 is communicated with the inlet of the first gas-liquid separator 17 through a sixth pipeline 16, so that the redundant heat of the second path of treated water generated by the second reaction tower 13 heats the mixture of the high-concentration high-salt-content organic wastewater passing through the first heat exchanger 9, the homogeneous catalyst and the air, thereby recovering the heat and saving the energy;
a gas phase outlet of the first gas-liquid separator 17 is communicated with an inlet of a first tail gas absorption tower 19 through a seventh pipeline 18, a liquid phase outlet of the first gas-liquid separator 17 is communicated with a feed inlet of a first buffer tank 21 through an eighth pipeline 20, a discharge outlet of the first buffer tank 21 is communicated with a feed inlet of an MVR evaporator 24 through a ninth pipeline 23 provided with a second diaphragm pump 22, a condensed water outlet of the MVR evaporator 24 is communicated with a feed inlet of a third heat exchanger 27 through a tenth pipeline 26 provided with a third diaphragm pump 25, a discharge outlet of the third heat exchanger 27 is communicated with an inlet of a third reaction tower 28, a top outlet of the third reaction tower 28 is communicated with a heat exchange water inlet of the third heat exchanger 27 through an eleventh pipeline 29, and a heat exchange water outlet of the third heat exchanger 27 is communicated with an inlet of a second gas-liquid separator 31 through a twelfth pipeline 30, so that redundant heat of three treated water generated by the third reaction tower 28 can add the condensed water passing through the third heat exchanger 27 The temperature is raised, thereby recovering heat and saving energy;
a gas-phase outlet of the second gas-liquid separator 31 is communicated with an inlet of the second tail gas absorption tower 33 through a thirteenth pipeline 32, and a liquid-phase outlet of the second gas-liquid separator 31 is communicated with a feed inlet of a second buffer tank 35 through a fourteenth pipeline 34; the air compressor 3 is communicated with the inlet of the pipeline mixer 6 through a third pipeline 8 so as to provide reaction air for the first reaction tower 10, and is also communicated with a fifteenth pipeline 36 communicated with the fourth pipeline 12 so as to provide reaction air for the second reaction tower 13, and is also communicated with a sixteenth pipeline 37 communicated with the tenth pipeline 26 so as to provide reaction air for the third reaction tower 28;
in this embodiment, the catalyst stored in the catalyst storage tank 2 is a homogeneous catalyst, and the homogeneous catalyst is one or more of ferric sulfate, ferric nitrate, copper sulfate, copper nitrate, manganese sulfate, manganese nitrate, cobalt sulfate, cobalt nitrate, zinc sulfate, zinc nitrate, nickel sulfate, and nickel nitrate, and the homogeneous catalyst can be used for better treating high-concentration high-salt organic wastewater, and has a good treatment effect;
in this embodiment, a heterogeneous catalyst is filled in the third reaction tower 28, the heterogeneous catalyst is a noble metal supported catalyst, a carrier of the heterogeneous catalyst is one or a combination of more of activated carbon, titanium dioxide, zirconium dioxide, aluminum oxide and a silicon dioxide molecular sieve, and an active component of the heterogeneous catalyst is one or more of ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum and neodymium, and the heterogeneous catalyst can be used for better treating high-concentration high-salt organic wastewater, so that the treatment effect is good;
the working principle of the wastewater treatment device is as follows:
firstly, the high-concentration high-salt organic wastewater stored in the wastewater storage tank 1 is introduced into the pipeline mixer 6 through the first pipeline 5 by the first diaphragm pump 4, meanwhile, the homogeneous catalyst stored in the catalyst storage tank 2 is also introduced into the pipeline mixer 6 through the second pipeline 7, meanwhile, the air for reaction is introduced into the pipeline mixer 6 through the third pipeline 8 by the air compressor 3, at the moment, the high-concentration high-salt organic wastewater, the homogeneous catalyst and the air are mixed in the pipeline mixer 6, then enter the first heat exchanger 9 from the feed inlet of the first heat exchanger 9, then enter the first reaction tower 10 from the discharge port of the first heat exchanger 9 for sufficient homogeneous catalysis wet oxidation reaction, the first reaction tower 10 discharges the primary treated water formed after the reaction into the fourth pipeline 12 from the top outlet of the first reaction tower 10, and then enters the feed inlet of the second heat exchanger 11 from the fourth pipeline 12, at this time, the air compressor 3 will introduce the air for reaction into the feed inlet of the second heat exchanger 11 through the fifteenth pipeline 36, the primary treated water from the first reaction tower 10 will be mixed with the air in the second heat exchanger 11 and fully exchanges heat with the water in the second heat exchanger 11, the water in the second heat exchanger 11 will be changed into steam for the turbine generator to generate electricity after heat exchange, the secondary treated water will be discharged into the second reaction tower 13 after heat exchange and temperature reduction for the second homogeneous catalysis wet oxidation reaction, the second reaction tower 13 will discharge the secondary treated water formed after reaction into the fifth pipeline 15 from the top outlet of the second reaction tower 13, then into the first heat exchanger 9 from the heat exchange water inlet of the first heat exchanger 9, then into the sixth pipeline 16 from the heat exchange water outlet of the first heat exchanger 9, during the process that the secondary treated water discharged from the second reaction tower 13 passes through the first heat exchanger 9, the waste heat of the second treated water is absorbed by the high-concentration high-salt organic wastewater passing through the first heat exchanger 9, the homogeneous catalyst and the air, so that the mixture of the high-concentration high-salt organic wastewater passing through the first heat exchanger 9, the homogeneous catalyst and the air is heated, and the mixture is gradually cooled after heat exchange;
at this time, the second treated water cooled and cooled in the sixth pipeline 16 enters the first gas-liquid separator 17 for gas-liquid separation, the first gas-liquid separator 17 discharges a gas phase generated after the second treated water-gas-liquid separation into the first tail gas absorption tower 19 through the seventh pipeline 18, the gas phase is treated by the first tail gas absorption tower 19 and discharged after reaching the standard, the first gas-liquid separator 17 discharges a liquid phase generated after the second treated water-gas-liquid separation into the first buffer tank 21 through the eighth pipeline 20, the liquid phase is pumped into the MVR evaporator 24 for treatment through the ninth pipeline 23 by the second diaphragm pump 22, the MVR evaporator 24 forms a distilled mother liquor and condensed water after treatment, wherein the distilled mother liquor can be used for recycling to prepare a homogeneous catalyst, the condensed water is pumped into the feed inlet of the third heat exchanger 27 through the tenth pipeline 26 by the third diaphragm pump 25, and at this time, the air compressor 3 feeds reaction air into the feed inlet of the third heat exchanger 27 through the sixteenth pipeline 37, the condensed water and air are mixed in the third heat exchanger 27 and then are introduced into the third reaction tower 28 from the discharge port of the third heat exchanger 27, and performs sufficient heterogeneous catalytic wet oxidation reaction together with the heterogeneous catalyst in the third reaction tower 28, the third reaction tower 28 discharges three treated water formed after reaction into an eleventh pipeline 29 from a top outlet, then enters the third heat exchanger 27 from a heat exchange water inlet of the third heat exchanger 27, and then discharges into a twelfth pipeline 30 from a heat exchange water outlet of the third heat exchanger 27, in the process that the three treated waters formed after the catalytic wet oxidation reaction discharged from the third reaction tower 28 pass through the third heat exchanger 27, the residual heat of the three treated waters is absorbed by the condensed water and air passing through the third heat exchanger 27, thereby heating the condensed water and air passing through the third heat exchanger 27, and gradually cooling down after heat exchange; the cooled three treated water flows into the twelfth pipeline 30 from the heat exchange port of the third heat exchanger 27, and then flows into the second gas-liquid separator 31 from the twelfth pipeline 30, the second gas-liquid separator 31 performs gas-liquid separation on the three treated water to generate a gas phase and a liquid phase, the generated gas phase is discharged into the second tail gas absorption tower 33 through the thirteenth pipeline 32 to be subjected to standard treatment and then is discharged, the generated liquid phase flows into the second buffer tank 21 through the fourteenth pipeline 34 and then is directly discharged into the outside from the second buffer tank 21 or enters a biochemical system for treatment, and through the above operations, the treatment of the high-concentration high-salt-content organic wastewater is completed.
The wastewater treatment device has the advantages that: (1) the treatment cost is low, the treatment effect is good, the occupied area is small, and the automation degree is high; (2) the wastewater with COD content over 10 ten thousand mg/L and high salt content can be directly treated without diluting the wastewater; (3) no secondary pollution to the environment exists in the wastewater treatment process; (4) the surplus heat is recovered through the heat exchanger, and the steam generated by the heat exchanger is used for generating power by the turbine generator, so that the purpose of energy recovery and utilization is achieved.
A method of wastewater treatment comprising the steps of:
(1) treating waste water of organic intermediate production, which mainly contains 1, 3-cyclohexanedione, sodium chloride and other components and has COD of 125360 mg/L, pH =3.5, salinity of 12.5%; mixing a homogeneous catalyst and wastewater, heating and introducing the mixture into a first reaction tower, and carrying out first homogeneous catalytic wet oxidation reaction on the wastewater mixed with the homogeneous catalyst and reaction air provided by an air compressor in the first reaction tower to generate primary treatment water containing the homogeneous catalyst; wherein the reaction conditions of the homogeneous catalysis wet oxidation reaction are as follows: the reaction temperature is 250-300 ℃, the reaction pressure is 4.5-9 MPa, and the liquid hourly space velocity is 0.5-3 h-1Wherein the adding amount of the homogeneous catalyst is 50-500 mg added per liter of wastewater;
(2) and (2) cooling the primary treated water generated in the step (1), introducing the primary treated water into a second reaction tower, and then carrying out a second homogeneous catalysis wet oxidation reaction on the primary treated water and reaction air provided by an air compressor in the second reaction tower to generate secondary treated water containing a homogeneous catalyst, wherein the reaction conditions of the homogeneous catalysis wet oxidation reaction are as follows: the reaction temperature is 220-290 ℃, the reaction pressure is 2.5-8 MPa, and the liquid hourly space velocity is 0.5-3 h-1Wherein the adding amount of the homogeneous catalyst is 50-500 mg added per liter of wastewater;
(3) then cooling the second treated water generated in the step (2), and introducing the cooled second treated water into a first gas-liquid separator for gas-liquid separation to generate a gas phase and a liquid phase containing a homogeneous catalyst;
(4) and (4) introducing the liquid phase generated in the step (3) into an MVR evaporator for evaporation to generate colorless crystalline salt, condensed water and a distilled mother liquor containing a homogeneous catalyst, wherein the evaporation conditions of the MVR evaporator are as follows: the evaporation temperature is (50-100) DEG C, and the amount of the mother liquor remained after evaporation is controlled to be (1-10)% of the amount of the liquid phase generated in the step (3);
(5) and (3) heating the condensed water generated in the step (4), introducing the heated condensed water into a third reaction tower, and carrying out heterogeneous catalytic wet oxidation reaction on the condensed water, a heterogeneous catalyst in the third reaction tower and reaction air provided by an air compressor in the third reaction tower to generate three treated waters, wherein the reaction conditions of the heterogeneous catalytic wet oxidation reaction are as follows: the reaction temperature is (180-280) DEG C, and the reaction pressure is (2).0 to 7.5) MPa and liquid hourly space velocity of (0.5 to 3) h-1；
(6) And (4) cooling the three treated water generated in the step (5), and introducing the cooled treated water into a second gas-liquid separator for gas-liquid separation to generate a gas phase and a liquid phase meeting the discharge standard.
The homogeneous catalyst is one or more of ferric sulfate, ferric nitrate, copper sulfate, copper nitrate, manganese sulfate, manganese nitrate, cobalt sulfate, cobalt nitrate, zinc sulfate, zinc nitrate, nickel sulfate and nickel nitrate.
The heterogeneous catalyst is a noble metal supported catalyst, the carrier of the heterogeneous catalyst is one or more of activated carbon, titanium dioxide, zirconium dioxide, aluminum oxide, silicon dioxide and molecular sieves, and the active component of the heterogeneous catalyst is one or more of ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum and neodymium.
The following table shows the COD, COD removal rate, salt content and PH value of the treated water obtained after the original wastewater is subjected to two homogeneous catalysis wet oxidation reactions and after the original wastewater is subjected to a heterogeneous catalysis wet oxidation reaction, and the good treatment effect of the wastewater treatment method can be seen from the table.
The wastewater treatment method has the advantages that: the treatment efficiency is good, the COD removal rate is high, the COD removal rate is greater than 95%, secondary pollution to the environment does not exist in the wastewater treatment process, wastewater with the COD content of more than 10 ten thousand mg/L and high salt content can be directly treated without diluting the wastewater, the method is particularly superior to treatment of wastewater with volatile organic components, the MVR evaporation mother liquor is recycled to prepare the homogeneous catalyst, the problem of concentrated solution is solved, the purpose of recycling is achieved, and precipitated salt is colorless clean salt and can be recycled.
Claims (9)
1. A method for treating wastewater, which is characterized in that: an energy recovery type wastewater catalytic wet oxidation treatment device is adopted, and the method comprises the following steps:
(1) mixing a homogeneous catalyst and wastewater, heating and introducing the mixture into a first reaction tower, and carrying out first homogeneous catalytic wet oxidation reaction on the wastewater mixed with the homogeneous catalyst and reaction air provided by an air compressor in the first reaction tower to generate primary treatment water containing the homogeneous catalyst;
(2) cooling the primary treated water generated in the step (1), introducing the primary treated water into a second reaction tower, and carrying out a second homogeneous catalysis wet oxidation reaction on the primary treated water and reaction air provided by an air compressor in the second reaction tower to generate secondary treated water containing a homogeneous catalyst;
(3) then cooling the second treated water generated in the step (2), and introducing the cooled second treated water into a first gas-liquid separator for gas-liquid separation to generate a gas phase and a liquid phase containing a homogeneous catalyst;
(4) then introducing the liquid phase generated in the step (3) into an MVR evaporator for evaporation to generate colorless crystalline salt, condensed water and a distilled mother liquor containing a homogeneous catalyst;
(5) heating the condensed water generated in the step (4), introducing the heated condensed water into a third reaction tower, and carrying out heterogeneous catalytic wet oxidation reaction on the condensed water, a heterogeneous catalyst in the third reaction tower and reaction air provided by an air compressor in the third reaction tower to generate three pieces of treated water;
(6) cooling the three treated water generated in the step (5), and introducing the cooled treated water into a second gas-liquid separator for gas-liquid separation to generate a gas phase and a liquid phase meeting the discharge standard;
the homogeneous catalyst is one or more of ferric sulfate, ferric nitrate, copper sulfate, copper nitrate, manganese sulfate, manganese nitrate, cobalt sulfate, cobalt nitrate, zinc sulfate, zinc nitrate, nickel sulfate and nickel nitrate;
the heterogeneous catalyst is a noble metal supported catalyst, the carrier of the heterogeneous catalyst is one or more of activated carbon, titanium dioxide, zirconium dioxide, aluminum oxide, silicon dioxide and molecular sieves, and the active component of the heterogeneous catalyst is one or more of ruthenium, rhodium, palladium, silver, platinum, cerium, lanthanum and neodymium;
the energy recovery type wastewater catalytic wet oxidation treatment device comprises a wastewater storage tank for storing wastewater, a catalyst storage tank for storing a catalyst and an air compressor, wherein a water outlet of the wastewater storage tank and a discharge port of the catalyst storage tank are simultaneously communicated with a feed port of a first heat exchanger, a discharge port of the first heat exchanger is communicated with an inlet of a first reaction tower, an outlet of the first reaction tower is communicated with a feed port of a second heat exchanger, a discharge port of the second heat exchanger is communicated with an inlet of a second reaction tower, a heat exchange water outlet of the second heat exchanger is connected with a turbine generator, an outlet of the second reaction tower is communicated with an inlet of a first gas-liquid separator through the first heat exchanger, a gas phase outlet of the first gas-liquid separator is communicated with an inlet of a first tail gas absorption tower, a liquid phase outlet of the first gas-liquid separator is communicated with a feed port of an MVR evaporator, and a condensed water outlet of the MVR, the discharge hole of the third heat exchanger is communicated with the inlet of a third reaction tower, the outlet of the third reaction tower is communicated with the inlet of a second gas-liquid separator through the third heat exchanger, and the gas-phase outlet of the second gas-liquid separator is communicated with the inlet of a second tail gas absorption tower; the air compressor simultaneously provides reaction air for the first reaction tower, the second reaction tower and the third reaction tower through pipelines.
2. The wastewater treatment method according to claim 1, characterized in that: the outlet of the second reaction tower is communicated with the shell layer of the first heat exchanger, the cold material and the hot material reversely flow through the first heat exchanger, and the shell layer outlet of the first heat exchanger is communicated with the inlet of the first gas-liquid separator.
3. The wastewater treatment method according to claim 1, characterized in that: the outlet of the third reaction tower is communicated with the shell of the third heat exchanger, the cold material and the hot material reversely flow through the third heat exchanger, and the outlet of the shell of the third heat exchanger is communicated with the inlet of the second gas-liquid separator.
4. The wastewater treatment method according to claim 1, characterized in that: the liquid phase outlet of the first gas-liquid separator is communicated with the feed inlet of the first buffer tank, and the discharge outlet of the first buffer tank is communicated with the feed inlet of the MVR evaporator.
5. The wastewater treatment method according to claim 1, characterized in that: and refluxing the distilled mother liquor of the MVR evaporator to the catalyst storage tank.
6. The wastewater treatment method according to claim 1, characterized in that: the reaction conditions of the homogeneous catalysis wet oxidation reaction in the step (1) are as follows: the reaction temperature is 250-300 ℃, the reaction pressure is 4.5-9 MPa, and the liquid hourly space velocity is 0.5-3 h-1Wherein the dosage of the homogeneous catalyst is 50-500 mg per liter of wastewater.
7. The wastewater treatment method according to claim 1, characterized in that: the reaction conditions of the homogeneous catalysis wet oxidation reaction in the step (2) are as follows: the reaction temperature is 220-290 ℃, the reaction pressure is 2.5-8 MPa, and the liquid hourly space velocity is 0.5-3 h-1Wherein the dosage of the homogeneous catalyst is 50-500 mg per liter of wastewater.
8. The wastewater treatment method according to claim 1, characterized in that: the evaporation conditions of the MVR evaporator in the step (4) are as follows: the evaporation temperature is 50-100 ℃, and the amount of the mother liquor remained after evaporation is controlled to be 1-10% of the amount of the liquid phase generated in the step (3).
9. The wastewater treatment method according to claim 1, characterized in that: the reaction conditions of the heterogeneous catalytic wet oxidation reaction in the step (5) are as follows: the reaction temperature is 180-280 ℃, the reaction pressure is 2.0-7.5 MPa, and the liquid hourly space velocity is 0.5-3 h-1。
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| CN108383231B (en) * | 2018-03-09 | 2021-01-12 | 涂学炎 | Method for double-phase catalytic treatment of high-salt high-concentration organic wastewater based on MVR system |
| CN109293116A (en) * | 2018-11-07 | 2019-02-01 | 苏州工业园区承叶环境科技有限公司 | A kind for the treatment of process of high concentration cymoxanil waste water |
| CN109179791A (en) * | 2018-11-16 | 2019-01-11 | 佛山科学技术学院 | A kind of catalytic wet oxidation processing equipment of the industrial wastewater with multistage filtering |
| CN112694163A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Method for quenching waste water of catalytic wet-type acrylonitrile oxidation device |
| CN110921806B (en) * | 2019-12-12 | 2022-04-01 | 山东沾化金嘉利化工科技有限公司 | Oxidation treatment method of calcium chloride-containing high-salinity wastewater |
| CN112456720B (en) * | 2021-01-25 | 2021-04-23 | 华夏碧水环保科技有限公司北京分公司 | CWO and MVR combined wastewater pretreatment system and pretreatment method |
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