CN114684955A - Treatment method and treatment device for ethylene waste alkali liquor - Google Patents
Treatment method and treatment device for ethylene waste alkali liquor Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 101
- 239000003513 alkali Substances 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 51
- 239000005977 Ethylene Substances 0.000 title claims abstract description 45
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 55
- 239000007789 gas Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 239000012071 phase Substances 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 238000005188 flotation Methods 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 238000012719 thermal polymerization Methods 0.000 claims description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 239000010865 sewage Substances 0.000 claims description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 150000004763 sulfides Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000003507 refrigerant Substances 0.000 claims description 5
- 238000009874 alkali refining Methods 0.000 claims description 4
- 239000013505 freshwater Substances 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 238000007667 floating Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- -1 diene hydrocarbon Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
-
- 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
- C02F2101/101—Sulfur 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- 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
- C02F2301/00—General aspects of water treatment
- C02F2301/06—Pressure conditions
- C02F2301/063—Underpressure, vacuum
-
- 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
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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 relates to a method and a device for treating ethylene waste alkali liquor, wherein the ethylene waste alkali liquor is treated by an air floatation unit and then enters a first heat exchanger of a heat exchange unit, the heated waste alkali liquor enters a wet oxidation unit and contacts with oxygen-containing gas under the condition that the solution keeps the pressure of a liquid phase to carry out wet oxidation reaction, the reacted material enters a second heat exchanger of the heat exchange unit, the heat-exchanged material is cooled and decompressed and then enters a gas-liquid separation unit, and the separated gas phase returns to the air floatation unit; the first heat exchanger and the second heat exchanger use the same heat exchange medium. According to the characteristics of the ethylene waste alkali liquor, the invention can avoid the problems of heat exchange equipment blockage and scaling, local over-temperature of a wet oxidation reactor and the like caused by long-term operation while fully utilizing reaction heat and reducing operation energy consumption.
Description
Technical Field
The invention belongs to the technical field of environmental protection waste water treatment, and particularly relates to a treatment method and a treatment device for ethylene waste alkali liquor.
Background
In the ethylene production process, it is common at presentRemoving CO in cracking gas by alkali washing method2、H2S, and the like. The alkaline washing process produces a large amount of spent lye which, in addition to the remaining NaOH, also contains Na which is formed during the alkaline washing process2S、Na2CO3And the like inorganic salts. Because the ethylene waste alkali liquor contains high-concentration COD and sulfides and has poor biodegradability, most of the treatment schemes at home and abroad for the ethylene waste alkali liquor are to carry out pretreatment to remove sulfides and organic matters in the ethylene waste alkali liquor so as to prevent the impact on a biochemical system of a sewage treatment plant.
CN98121081.3 discloses a method for treating waste alkali liquor of oil alkali refining in petroleum refining industry, which comprises subjecting waste alkali liquor discharged from oil alkali refining unit in petroleum refining process, mainly containing inorganic sulfide, organic sulfide, phenols and naphthenic acids, to wet liquid phase oxidation to convert sulfur therein into sulfate and/or thiosulfate, then depressurizing and cooling the oxidized waste alkali liquor, adding acid to acidify and recover phenol and naphthenic acid therein, treating the obtained waste water with intermittent activated sludge process (SBR), and controlling salt content in the waste water entering SBR biological reaction tank below 30 g/L. The method does not produce air pollution, the device is light in corrosion, and can realize the desulfurization and deodorization of the waste alkali liquor, but the reaction temperature is maintained by supplementing a large amount of steam into the reactor, so the device has higher energy consumption in operation.
In order to reduce the operation energy consumption and realize effective utilization of heat, researchers propose that a heat exchanger is arranged in front of a wet oxidation reactor, and materials after wet oxidation are used for preheating imported waste alkali liquor so as to reduce the steam consumption of a reaction device.
US20050171390a1 discloses a wet oxidation treatment process and system, in which a wastewater of one or more compounds having carbon-heteroatom bonds is subjected to wet oxidation treatment at high temperature and high pressure to break the carbon-heteroatom bonds of at least one of the compounds, and the treated wastewater is passed to a subsequent advanced oxidation system. According to the technology, a mode of mixing waste alkali liquor and air for oxidation to preheat feeding is adopted, on one hand, substances which are easy to generate thermal polymerization exist in the ethylene waste alkali liquor, high polymers can be generated in the subsequent preheating process, and the heat exchanger can be blocked in the long-term operation process; and because the air contains oxygen, the oxygen can participate in the formation of peroxide self-polymerization to further form high polymer, thereby promoting the blockage of the heat exchanger. In addition, the polymer-containing waste lye enters a subsequent wet oxidation reactor, and the long-term operation can cause the blockage and local overtemperature of the wet oxidation reactor, thereby affecting the treatment effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method and a device for treating ethylene waste lye. According to the characteristics of the ethylene waste alkali liquor, the invention can avoid the problems of heat exchange equipment blockage and scaling, local over-temperature of a wet oxidation reactor and the like caused by long-term operation while fully utilizing reaction heat and reducing operation energy consumption.
The invention provides a method for treating ethylene waste alkali liquor, which comprises the following steps:
after being treated by the air floatation unit, the ethylene waste alkali liquor enters a first heat exchanger of a heat exchange unit, the heated waste alkali liquor enters a wet oxidation unit, is contacted with oxygen-containing gas under the condition that the solution keeps the pressure of a liquid phase, is subjected to wet oxidation reaction, the reacted material enters a second heat exchanger of the heat exchange unit, the heat-exchanged material enters a gas-liquid separation unit after being cooled and decompressed, and the separated gas phase returns to the air floatation unit; the first heat exchanger and the second heat exchanger use the same heat exchange medium, and the medium is used as a heat medium in the first heat exchanger and is used as a refrigerant in the second heat exchanger.
In the invention, the ethylene waste alkali liquor is waste alkali liquor containing sulfide and COD generated in the ethylene cracking gas alkali refining process, wherein the COD is 6000-100000mg/L, S2-The concentration is 2000-50000mg/L, and the material which is easy to generate thermal polymerization is also contained, specifically, the material of diene hydrocarbon is at least one of butadiene, isoprene and the like.
In the invention, the air floating unit can adopt a conventionally used air floating tank and the like, the air used for air floating can be air and the like, and preferably, the gas generated after gas-liquid separation is adopted, and the residual heat of the gas is helpful for removing substances which are easy to generate thermal polymerization in the gas.
In the invention, the heat exchange medium can be at least one of fresh water, circulating water, deoxygenated water and the like, and preferably deoxygenated water.
In the invention, the temperature of the waste alkali liquor after heat exchange by the first heat exchanger is controlled to be 80-190 ℃, and the temperature is preferably 140-170 ℃.
In the present invention, the reactor of the wet oxidation unit is preferably a sleeve type internal circulation reactor, and air is directly introduced into the reactor to realize sufficient mixing. The reaction temperature of the wet oxidation reaction is 130-220 ℃, preferably 180-200 ℃, the reaction pressure is 1.5-4.5MPa, preferably 2.5-3.5MPa, and the reaction time is 0.5-3.0h, preferably 1.0-2.0 h.
In the invention, the waste alkali liquor is introduced into the wet oxidation unit and simultaneously introduced with air, wherein the air amount is 100-300 percent of the air amount required by the complete oxidation of COD in the waste alkali liquor, and is preferably 110-200 percent. In the wet oxidation unit, the oxygen oxidizes the sulfides in the waste alkali liquor into sulfates and thiosulfates, and the organic matters are oxidized into low-molecular organic acids.
In the invention, if the COD concentration in the waste alkali liquor is lower, the oxidation reaction is insufficient in heat release, and superheated steam can be introduced into the wet oxidation reactor to supplement heat.
In the invention, the material treated by the wet oxidation unit enters the second heat exchanger, and the temperature of the waste alkali liquor after heat exchange is controlled to be 60-140 ℃. Cooling and decompressing the material after heat exchange to 30-50 ℃ and decompressing to 0.35-0.5 MPa.
In the invention, the waste alkali liquor after cooling and pressure reduction is conveyed to the gas-liquid separation unit, and the separated liquid phase enters a sewage treatment field, and the sulfide is effectively treated, so that the sewage treatment is not influenced. The temperature of the separated gas phase is 30-50 ℃, and the gas phase is conveyed to the air flotation unit and used as the introduced gas of the air flotation unit, which is beneficial to removing diolefin substances.
According to the invention, the same heat exchange medium is used for the first heat exchanger and the second heat exchanger, a heat exchange medium storage tank is arranged between the first heat exchanger and the second heat exchanger, the heat exchange medium enters the heat exchange medium storage tank, enters the second heat exchanger through a heat exchange medium circulating pump, exchanges heat with the material at the outlet of the wet oxidation reactor, enters the first heat exchanger after the temperature of the heat exchange medium is raised, exchanges heat with the waste alkali liquor treated by the air floatation unit, and returns to the heat exchange medium storage tank after the temperature is lowered.
The invention also provides a treatment device for the treatment method of the ethylene waste alkali liquor, which mainly comprises an air flotation unit, a heat exchange unit, a wet oxidation unit and a gas-liquid separation unit, wherein the air flotation unit is used for removing substances which are easy to generate thermal polymerization, the heat exchange unit comprises a first heat exchanger, a heat exchange medium storage tank and a second heat exchanger and is used for exchanging heat among materials discharged by the wet oxidation unit, the heat exchange medium and the fed waste alkali liquor, the wet oxidation unit is used for converting sulfides in the waste alkali liquor into sulfate and thiosulfate, the oxidized materials enter the second heat exchanger for heat exchange, the materials after heat exchange are cooled and decompressed and then enter the gas-liquid separation unit, the separated gas phase is conveyed to the air flotation unit, and the liquid phase enters a sewage treatment field.
Compared with the prior art, the invention has the following beneficial effects:
(1) when the wet oxidation process is used for treating the ethylene waste alkali liquor, in order to realize heat utilization, researchers design a heat exchanger in front of a reactor, and directly heat the imported waste alkali liquor by using materials discharged from the reactor. However, the inventor of the present application finds that the heat exchanger may be blocked and scaled along with the long-term operation of the treatment device, and finds that the heat exchanger is caused by some polymerization substances through analysis reasons, on the basis of the research and discovery, the inventor sets an air flotation treatment unit in front of the heat exchanger, removes organic matters which are easy to generate thermal polymerization in the heat exchanger by using air flotation gas, and simultaneously exchanges heat with materials at a wet oxidation inlet and outlet by combining an indirect heat exchange mode, thereby avoiding the problems of blocking and scaling of the heat exchanger and subsequent blocking and local over-temperature and the like in a wet oxidation reactor on the basis of realizing the full utilization of heat, ensuring the long-term stable operation of the device, and reducing the energy consumption of the operation of the device.
(2) Aiming at the problem of organic matter thermal polymerization of ethylene waste alkali liquor in a heat exchanger, the inventor sets air floatation treatment in front of the heat exchanger, and simultaneously adopts tail gas after gas-liquid separation as air floatation gas, thereby being beneficial to efficiently removing organic matters which are easy to generate thermal polymerization in the waste alkali liquor and avoiding the blockage of the heat exchanger.
(3) Establish first heat exchanger and second heat exchanger and use same heat transfer medium, avoid wet-type oxidation discharge material directly as the heat medium, effectively avoided the heat exchanger scale deposit problem that direct heat transfer caused, guarantee the long period operation of device.
(4) By adopting the sleeve type internal circulation reactor, the temperature in the reactor is uniform, the problem of blockage is avoided, and simultaneously the gas-liquid mass transfer efficiency and the oxidation effect can be ensured.
Drawings
FIG. 1 is a schematic process flow diagram of the present invention;
wherein: 101-ethylene waste alkali liquid, 102-compressed air, 103-steam, 104-gas phase tail gas, 105-treated waste alkali liquid; 201-an air flotation tank, 202-a waste lye feed pump, 203-a heat exchange medium circulating pump, 204-a heat exchange medium storage tank, 205-a first heat exchanger, 206-a second heat exchanger, 207-a wet oxidation reactor, 208-a cooler and 209-a gas-liquid separator.
Detailed Description
The processing method, apparatus and effect of the present invention will be described in further detail by way of examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
The processing device adopted by the embodiment of the invention is shown in figure 1 and mainly comprises an air flotation unit, a heat exchange unit, a wet oxidation unit and a gas-liquid separation unit, wherein the air flotation unit mainly comprises an air flotation tank 201, the heat exchange unit comprises a first heat exchanger 205, a heat exchange medium storage tank 204 and a second heat exchanger 206, the wet oxidation unit mainly comprises a wet oxidation reactor 207, the gas-liquid separation unit comprises a cooler 208 and a gas-liquid separator 209, ethylene waste alkali liquor enters the air flotation tank 201 for processing and used for removing substances which are easy to generate thermal polymerization, the processed waste alkali liquor is conveyed to the first heat exchanger 205 through a waste alkali liquor feeding pump 202, the heated waste alkali liquor enters the wet oxidation reactor 207 and contacts with oxygen-containing gas under the condition that the solution keeps a liquid phase, sulfides in the waste alkali liquor are converted into sulfates and thiosulfates, the oxidized materials enter the second heat exchanger 206 and exchange heat with the discharged material of the wet oxidation reactor, the heat-exchanged materials pass through the cooler 208 and then enter the gas-liquid separator, the separated gas phase returns to the gas floating tank 201, and the liquid phase enters the sewage treatment plant. The first heat exchanger and the second heat exchanger use the same heat exchange medium, a heat exchange medium storage tank is arranged between the first heat exchanger and the second heat exchanger, the heat exchange medium enters the heat exchange medium storage tank, enters the second heat exchanger through a heat exchange medium circulating pump, exchanges heat with the material at the outlet of the wet oxidation reactor, enters the first heat exchanger after the heat exchange medium is heated up, exchanges heat with the waste alkali liquor treated by the air floatation unit, and returns to the heat exchange medium storage tank after the heat exchange medium is cooled down.
In the invention, the COD detection method is a method specified by HJ 828-2017 (dichromate determination method for water quality chemical oxygen demand); s2-The detection method (2) is a method defined in HJ-T60-2000 (iodine method for measuring sulfide in water).
Example 1
The ethylene waste alkali liquor treated by the embodiment is waste alkali liquor discharged in the alkali washing process of ethylene cracking gas of a certain factory, wherein the COD concentration is 35000mg/L, and S is2-The concentration is 15200mg/L, and the petroleum is 1320mg/L, wherein the petroleum comprises substances such as butadiene, isoprene and the like.
The treatment process and the device shown in figure 1 are adopted for treatment, ethylene waste lye is conveyed to an air flotation tank for air flotation treatment, gas obtained by gas-liquid separation in the process is introduced to be used as air flotation gas, and diolefin substances in the waste lye are removed.
The method comprises the steps that deoxygenated water serving as a heat exchange medium enters a heat exchange medium storage tank and is lifted to a second heat exchanger through a heat exchange medium circulating pump, the deoxygenated water serving as a refrigerant exchanges heat with discharged materials of a reactor, and the deoxygenated water after being heated up enters a first heat exchanger as a heat medium.
After air flotation treatment, the waste alkali liquor is conveyed to a first heat exchanger through a feed pump, enters a wet oxidation reactor after heat exchange is carried out to 160 ℃, and reacts with introduced compressed air, wherein the wet oxidation reactor adopts a sleeve type internal circulation reactor, the air quantity is 150% of the air quantity required by complete oxidation of COD (chemical oxygen demand) in the waste alkali liquor, the reaction temperature is 190 ℃, the reaction pressure is 3.0MPa, and the reaction time is 2.0 hours. In the wet oxidation reactor, the oxygen molecules oxidize the sulfide in the waste alkali liquor into sulfate and thiosulfate, and the organic matters are oxidized into low-molecular organic acid.
And (3) after the ethylene waste alkali liquid subjected to wet oxidation treatment enters a second heat exchanger for heat exchange to 110 ℃, the ethylene waste alkali liquid is cooled to 45 ℃ by a cooler, the ethylene waste alkali liquid is decompressed to 0.4MPa and then enters a gas-liquid separator for gas-liquid separation, the separated gas phase is introduced into an air flotation tank for air flotation treatment of the fed waste alkali liquid, and the separated liquid phase can be directly discharged into a sewage treatment plant after neutralization treatment.
By adopting the treatment process, the heat exchanger does not have the blockage phenomenon after 2000 hours of operation. In the water S2-The concentration is less than 1.0mg/L, and the COD is less than 1500 mg/L. If the air floatation treatment is not arranged, the heat exchanger is blocked after the operation for the same time, the waste alkali liquor can only be subjected to heat exchange to 130 ℃, steam needs to be supplemented into the reactor to maintain the reaction temperature, and the COD concentration of the effluent is 3000-4000 mg/L.
Example 2
The ethylene waste alkali liquor treated by the embodiment is waste alkali liquor discharged in the alkali washing process of ethylene cracking gas of a certain factory, wherein the COD concentration is 10000mg/L, and S is2-The concentration is 3700mg/L, and the petroleum is 650mg/L, wherein the petroleum comprises substances such as butadiene, isoprene and the like.
The treatment process and the device shown in figure 1 are adopted for treatment, ethylene waste lye is conveyed to an air flotation tank for air flotation treatment, gas obtained by gas-liquid separation in the process is introduced to be used as air flotation gas, and diolefin substances in the waste lye are removed. The method comprises the steps that deoxygenated water serving as a heat exchange medium enters a heat exchange medium storage tank and is lifted to a second heat exchanger through a heat exchange medium circulating pump, the deoxygenated water serving as a refrigerant exchanges heat with discharged materials of a reactor, and the deoxygenated water after being heated up enters a first heat exchanger as a heat medium.
After air flotation treatment, the waste alkali liquor is conveyed to a first heat exchanger through a feed pump, enters a wet oxidation reactor after heat exchange is carried out to 120 ℃, and reacts with introduced compressed air, wherein the wet oxidation reactor adopts a sleeve type internal circulation reactor, the air quantity is 110% of the air quantity required by complete oxidation of COD (chemical oxygen demand) in the waste alkali liquor, the reaction temperature is 150 ℃, the reaction pressure is 3.0MPa, and the reaction time is 2.0 hours. In the wet oxidation reactor, the oxygen molecules oxidize the sulfide in the waste alkali liquor into sulfate and thiosulfate, and the organic matter is oxidized into low-molecular organic acid.
And (3) after the ethylene waste alkali liquid subjected to wet oxidation treatment enters a second heat exchanger for heat exchange to 70 ℃, the ethylene waste alkali liquid is cooled to 35 ℃ by a cooler, the ethylene waste alkali liquid is decompressed to 0.35MPa and then enters a liquid separation tank for gas-liquid separation, the separated gas phase is introduced into an air flotation tank for air flotation treatment of the raw material waste alkali liquid, and the separated liquid phase can be directly discharged into a sewage treatment plant after neutralization treatment.
By adopting the treatment process, the heat exchanger does not have the blockage phenomenon after 2000 hours of operation. Goes out in water S2-The concentration is less than 15mg/L, and the COD is less than 2000 mg/L. If the air floatation treatment is not set, the heat exchanger is blocked after the operation for the same time, the waste alkali liquor can only be subjected to heat exchange to 90 ℃, steam needs to be supplemented into the reactor to maintain the reaction temperature, and the COD concentration of the effluent is 2500 mg/L.
Example 3
The ethylene waste alkali liquor treated by the embodiment is waste alkali liquor discharged from an ethylene cracking gas alkali washing process of a certain factory, wherein the COD concentration is 50000mg/L, and S2-The concentration is 22000mg/L, and the petroleum is 1530mg/L, wherein the petroleum comprises substances such as butadiene, isoprene and the like.
The treatment process and the device shown in figure 1 are adopted for treatment, ethylene waste lye is conveyed to an air flotation tank for air flotation treatment, gas obtained by gas-liquid separation in the process is introduced to be used as air flotation gas, and diolefin substances in the waste lye are removed. The method comprises the steps that deoxygenated water serving as a heat exchange medium enters a heat exchange medium storage tank and is lifted to a second heat exchanger through a heat exchange medium circulating pump, the deoxygenated water serving as a refrigerant exchanges heat with discharged materials of a reactor, and the deoxygenated water after being heated up enters a first heat exchanger as a heat medium.
After air flotation treatment, the waste alkali liquor is conveyed to a first heat exchanger through a feed pump, enters a wet oxidation reactor after heat exchange is carried out to 190 ℃, and reacts with introduced compressed air, wherein the wet oxidation reactor adopts a sleeve type internal circulation reactor, the air quantity is 200% of the air quantity required by complete oxidation of COD (chemical oxygen demand) in the waste alkali liquor, the reaction temperature is 220 ℃, the reaction pressure is 4.5MPa, and the reaction time is 2.0 hours. In the wet oxidation reactor, the oxygen molecules oxidize the sulfide in the waste alkali liquor into sulfate and thiosulfate, and the organic matter is oxidized into low-molecular organic acid.
And (3) after the ethylene waste alkali liquid subjected to wet oxidation treatment enters a second heat exchanger for heat exchange to 140 ℃, the ethylene waste alkali liquid is cooled to 50 ℃ by a cooler, the ethylene waste alkali liquid is decompressed to 0.5MPa and then enters a liquid separation tank for gas-liquid separation, the separated gas phase is introduced into an air flotation tank for air flotation treatment of the raw material waste alkali liquid, and the separated liquid phase can be directly discharged into a sewage treatment plant after neutralization treatment.
By adopting the treatment process, the heat exchanger does not have the blockage phenomenon after 2000 hours of operation. In the water S2-The concentration is less than 1.0mg/L, and the COD is less than 2500 mg/L. If the air floatation treatment is not carried out, the heat exchanger is blocked after the operation for the same time, the waste alkali liquor can only be subjected to heat exchange to 160 ℃, steam needs to be supplemented into the reactor to maintain the reaction temperature, and the COD concentration of the effluent is 4000 mg/L.
Example 4
The difference from example 1 is that: the air floating unit adopts air as air floating gas. By adopting the treatment process, the heat exchanger does not have the blockage phenomenon after 2000 hours of operation. In the water S2-The concentration is less than 1.0mg/L, COD and less than 2000 mg/L.
Example 5
The difference from example 1 is that: fresh water is used as a heat exchange medium. The device is operated for 2000 hours, and only the waste alkali liquor can be subjected to heat exchange to 155 ℃. In the water S2-The concentration is less than 1.0mg/L, COD and less than 1500 mg/L.
Claims (14)
1. The method for treating the ethylene waste alkali liquor is characterized by comprising the following steps of: after being treated by the air floatation unit, the ethylene waste alkali liquor enters a first heat exchanger of a heat exchange unit, the heated waste alkali liquor enters a wet oxidation unit, is contacted with oxygen-containing gas under the condition that the solution keeps the pressure of a liquid phase, is subjected to wet oxidation reaction, the reacted material enters a second heat exchanger of the heat exchange unit, the heat-exchanged material enters a gas-liquid separation unit after being cooled and decompressed, and the separated gas phase returns to the air floatation unit; the first heat exchanger and the second heat exchanger use the same heat exchange medium, and the medium is used as a heat medium in the first heat exchanger and is used as a refrigerant in the second heat exchanger.
2. The method of claim 1, wherein: the ethylene waste alkali liquor is waste alkali liquor containing sulfide and COD generated in the ethylene cracking gas alkali refining process, wherein the COD is 6000-100000mg/L, S2-The concentration is 2000-50000mg/L, and the material which is easy to generate thermal polymerization is contained.
3. The method of claim 2, wherein: the material which is easy to generate thermal polymerization is a diolefin material, and the diolefin material is at least one of butadiene and isoprene.
4. The method of claim 1, wherein: the heat exchange medium is at least one of fresh water, circulating water, deoxygenated water and the like, and preferably deoxygenated water.
5. The method of claim 1, wherein: the temperature of the waste alkali liquor after heat exchange through the first heat exchanger is controlled to be 80-190 ℃, and the temperature is preferably 140-170 ℃.
6. The method of claim 1, wherein: the reactor of the wet oxidation unit adopts a sleeve type internal circulation reactor, and air is directly introduced into the reactor to realize full mixing.
7. The method according to claim 1 or 6, characterized in that: the reaction temperature of the wet oxidation unit is 130-220 ℃, preferably 180-200 ℃, the reaction pressure is 1.5-4.5MPa, preferably 2.5-3.5MPa, and the reaction time is 0.5-3.0h, preferably 1.0-2.0 h.
8. The method of claim 1, wherein: and introducing air while introducing the waste alkali liquor into the wet oxidation unit, wherein the air amount is 100-300%, preferably 110-200% of the air amount required by the complete oxidation of COD in the waste alkali liquor.
9. The method of claim 1, wherein: if the COD concentration in the waste alkali liquor is lower, the heat release of the oxidation reaction is insufficient, and superheated steam is introduced into the wet oxidation reactor to supplement heat.
10. The method of claim 1, wherein: the material treated by the wet oxidation unit enters a second heat exchanger, and the temperature of the waste alkali liquor after heat exchange is controlled to be 60-140 ℃.
11. The method according to claim 1 or 10, characterized in that: cooling and decompressing the material after heat exchange to 30-50 ℃ and decompressing to 0.35-0.5 MPa.
12. The method of claim 1, wherein: and conveying the waste alkali liquor to a gas-liquid separation unit after cooling and pressure reduction, wherein the temperature of a separated gas phase is 30-50 ℃, and conveying the gas phase to an air floatation unit for introducing gas into the air floatation unit.
13. The method of claim 1, wherein: the first heat exchanger and the second heat exchanger use the same heat exchange medium, a heat exchange medium storage tank is arranged between the first heat exchanger and the second heat exchanger, the heat exchange medium enters the heat exchange medium storage tank, enters the second heat exchanger through a heat exchange medium circulating pump, exchanges heat with the material at the outlet of the wet oxidation reactor, enters the first heat exchanger after the heat exchange medium is heated up, exchanges heat with the waste alkali liquor treated by the air floatation unit, and returns to the heat exchange medium storage tank after the heat exchange medium is cooled down.
14. A treatment device for the treatment method of the ethylene waste alkali liquor as claimed in any one of claims 1 to 13, which is characterized by mainly comprising an air flotation unit, a heat exchange unit, a wet oxidation unit and a gas-liquid separation unit, wherein the air flotation unit is used for removing substances which are easy to generate thermal polymerization, the heat exchange unit comprises a first heat exchanger, a heat exchange medium storage tank and a second heat exchanger and is used for exchanging heat among materials discharged by the wet oxidation unit, the heat exchange medium and fed waste alkali liquor, the wet oxidation unit is used for converting sulfides in the waste alkali liquor into sulfate and thiosulfate, the oxidized materials are subjected to heat exchange in the second heat exchanger, the materials subjected to heat exchange are cooled and decompressed and then enter the gas-liquid separation unit, and a gas phase after separation is conveyed to the air flotation unit and a liquid phase enters a sewage treatment field.
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| EP0787690A2 (en) * | 1996-01-31 | 1997-08-06 | Nippon Petrochemicals Co., Ltd. | Wet oxidizing process of waste soda |
| CN101164913A (en) * | 2006-07-04 | 2008-04-23 | 林德股份公司 | Oxidation method and equipment for spent caustic in petrochemistry equipment |
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