CN117550736A - Treatment method of petroleum refining industrial oil product refined waste alkali liquor - Google Patents
Treatment method of petroleum refining industrial oil product refined waste alkali liquor Download PDFInfo
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- CN117550736A CN117550736A CN202311503707.XA CN202311503707A CN117550736A CN 117550736 A CN117550736 A CN 117550736A CN 202311503707 A CN202311503707 A CN 202311503707A CN 117550736 A CN117550736 A CN 117550736A
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- 239000002699 waste material Substances 0.000 title claims abstract description 99
- 239000003513 alkali Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000003921 oil Substances 0.000 title claims abstract description 30
- 238000005504 petroleum refining Methods 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 238000001816 cooling Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 230000008020 evaporation Effects 0.000 claims abstract description 9
- 238000011033 desalting Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000012071 phase Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000007791 liquid phase Substances 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 8
- 238000009279 wet oxidation reaction Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 230000005587 bubbling Effects 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 239000000498 cooling water Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000012855 volatile organic compound Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006386 neutralization reaction Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 6
- 239000001294 propane Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 29
- 239000002351 wastewater Substances 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000010802 sludge Substances 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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 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
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F2103/365—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 from petrochemical industry (e.g. refineries)
Landscapes
- 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 treatment method of refined waste alkali liquid of petroleum refining industrial oil products, which comprises the following steps: 1) Conveying sodium hydroxide solution and waste alkali liquor through a storage tank for mixing; 2) Adding the mixed solution into a reactor for oxidation reaction; 3) And (3) performing gas-liquid separation on the waste alkali liquid after the oxidation reaction by a circulating cooling tower. The method for treating the refined waste alkali liquid of the petroleum refining industrial oil products combines the water quality characteristics of the waste alkali liquid, develops a treatment technology of adding alkali into the propane dehydrogenation waste alkali liquid, carrying out wet oxidation-acidification neutralization, after the treatment by the device, the S2-mass concentration of the effluent of the propane dehydrogenation waste alkali liquid is less than 1mg/L, the COD is less than 200mg/L, the malodorous smell of the waste alkali liquid is completely removed, the tail gas of the device meets the national emission requirements, the oxidized waste alkali liquid and the neutralization water with the pH value of 6 to 9 mixed by ninety-eight percent concentrated sulfuric acid can be directly treated by an evaporation desalting process, and the environmental benefit and the economic benefit are obvious.
Description
Technical Field
The invention relates to the technical field of petroleum refining, in particular to a treatment method of petroleum refining industrial oil product refined waste alkali liquor.
Background
The waste alkali liquid is mainly from alkaline waste liquid containing a large amount of sulfide, mercaptan, phenols, petroleum, naphthenic acid and other toxic and harmful pollutants, which is generated during the alkaline washing and refining of products such as gasoline, diesel oil, liquefied gas and the like in the petroleum refining process, and is black brown and has malodorous smell, and the water quality condition of the general oil refining alkali slag is as follows: the sulfide mass concentration is >8000mg/L, the phenol mass concentration is >2000mg/L, the COD mass concentration is >20000mg/L, and the pH value is above 12, so that the wastewater has high pollutant concentration and high alkalinity and has similar properties to solid pollutants, and is commonly called as oil refining alkaline residues, the discharge amount of the oil refining alkaline residues wastewater is not large and accounts for 5 to 10 percent of the discharge amount of the oil refining wastewater, but the discharge amount of pollutants such as COD, sulfide, phenols and the like accounts for 20 to 50 percent of the discharge amount of the pollutants of the oil refinery, and the wastewater becomes a main malodorous pollution source of the oil refinery.
In the treatment method of the oil refining waste lye disclosed in Chinese patent publication No. (CN 109942108B), the oil refining waste lye is subjected to sulfuric acid acidification, a gas phase generated by the acidification is used for Fenton sludge reduction, and an oil phase is recovered after the liquid phase is settled; fenton oxidation treatment is carried out on the waste alkali liquor after the oil phase is recovered; adding sodium hydroxide into the waste alkali liquid after Fenton oxidation, and recovering precipitated sodium sulfate; the sludge produced by Fenton oxidation is dissolved by adding acid and added with alkali to adjust pH, then is used for absorbing acid gas produced by sulfuric acid acidification, and liquid phase is recycled to Fenton oxidation after solid-liquid separation.
However, the problem of poor treatment, separation and removal effects on the waste lye also exists in the above patent, and the treatment method for the waste lye in the above patent mainly comprises the steps of adding acidic substances to treat alkaline residues, adopting a neutralization method, discharging the alkaline residues into an oily sewage treatment field, inhibiting the growth and reproduction of microorganisms after the alkaline residues with high concentration enter an oily sewage biochemical treatment system, and dying a large amount of microorganisms when serious, thereby influencing the normal operation of the sewage treatment field and the standard discharge of wastewater.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a treatment method of the refined waste alkali liquid of the petroleum refining industrial oil product, which has the advantages of good treatment and separation effects and the like, and solves the problem of poor treatment and separation and removal effects of the waste alkali liquid in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions: a treatment method of petroleum refining industrial oil product refined waste alkali liquid comprises the following steps:
1) Conveying sodium hydroxide solution and waste alkali liquor through a storage tank for mixing;
2) Adding the mixed solution into a reactor for oxidation reaction;
3) Performing gas-liquid separation on the waste alkali liquid after the oxidation reaction by a circulating cooling tower;
4) The liquid phase is discharged to a heat exchanger for cooling through the bottom of the tower;
5) The separated gas phase mixture moves to the upper part of the tower, contacts with the refluxed cold alkali liquor, is condensed and cooled, and the rest gas phase mixture is discharged from the top of the tower;
6) The waste alkali liquid after oxidation is neutralized and then is treated by an evaporation desalting process, so that zero emission of the waste alkali liquid is realized.
Further, the step 1 of mixing the waste alkali solution comprises the steps of mixing the waste alkali solution with thirty-two percent sodium hydroxide solution, pressurizing by a feed pump, and introducing the mixture into a ring system between an inner cylinder and an outer cylinder of the reactor from the upper part of the reactor to perform oxidation reaction.
Further, the oxidation reaction in the step 2 comprises that waste lye enters an annular gap between an inner cylinder and an outer cylinder of the reactor through two symmetrical feed inlets at the upper part of the reactor, compressed air enters the inner cylinder from the bottom of the reactor through a distributor in a bubbling flow mode, and high-temperature internal circulation is formed due to the difference of gas contents between the inner cylinder and the outer cylinder and the air lift effect, and the feed waste lye is preheated in the circulation process, so that harmful substances are oxidatively decomposed.
Further, the gas-liquid separation in the step 3 comprises inner components such as a tray, a feed rectifier and a gas rising pipe, and the like, and the circulating cooling tower is used for condensing and cooling the reacted materials, and the residual alkalinity of the waste alkali liquid after the wet oxidation treatment is utilized to carry out alkaline washing on the tail gas through the design of the internal structure of the washing tower, so that the tail gas can reach the standard and be discharged through the water washing process.
Further, the reacted material is discharged from the top of the reactor, and enters a circulating cooling tower after being decompressed, and air entering the tower and oxidized waste alkali liquid are subjected to gas-liquid separation at first.
Further, the separated gas phase mixture moves to the upper part of the tower and contacts with the back-flowing cold alkali liquor, the water vapor and volatile organic compounds in the gas phase mixture are condensed and cooled, the gas phase mixture returns to the bottom of the tower, and the rest gas phase mixture is discharged from the top of the tower.
Further, the oxidized waste alkali liquor and ninety-eight percent concentrated sulfuric acid are mixed to the neutralized water with the pH value of 6 to 9, and zero emission of the waste alkali liquor can be realized after the waste alkali liquor is directly treated by an evaporation desalting process.
Further, the heat exchanger is a cylindrical and horizontal shell-and-tube heat exchanger, the tube side inlet receives oxidized waste lye from the outlet of the circulating cooling tower, and the shell side adopts circulating cooling water from public engineering as a heat exchange medium to reduce the temperature of the oxidized waste lye to below 40 ℃.
Further, the oxidation reaction in the step 2 adopts a wet oxidation reactor, which adopts a sleeve type bubbling flow internal circulation reactor, which is a vertical reactor with an inner cylinder, and waste alkali liquid enters an annular space between the inner cylinder and the outer cylinder of the reactor through two symmetrical feed inlets at the upper part of the reactor.
Further, the liquid phase is discharged to a heat exchanger through the bottom of the tower, a part of the cooled liquid phase flows back to the middle upper part of the tower, and the other part of the cooled liquid phase enters the oxidized waste lye storage tank.
Compared with the prior art, the technical scheme of the application has the following beneficial effects:
the method for treating the refined waste alkali liquid of the petroleum refining industrial oil products combines the water quality characteristics of the waste alkali liquid, develops a treatment technology of adding alkali into the propane dehydrogenation waste alkali liquid, carrying out wet oxidation-acidification neutralization, after the treatment by the device, the S2-mass concentration of the effluent of the propane dehydrogenation waste alkali liquid is less than 1mg/L, the COD is less than 200mg/L, the malodorous smell of the waste alkali liquid is completely removed, the tail gas of the device meets the national emission requirements, the oxidized waste alkali liquid and the neutralization water with the pH value of 6 to 9 mixed by ninety-eight percent concentrated sulfuric acid can be directly treated by an evaporation desalting process, and the environmental benefit and the economic benefit are obvious.
Drawings
FIG. 1 is a flow chart of the steps of the structure of the present invention;
FIG. 2 is a flow chart of the structural process of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1-2, a treatment method of refined waste alkali solution of petroleum refining industrial oil product in this embodiment includes the following steps:
1) Conveying sodium hydroxide solution and waste alkali liquor through a storage tank for mixing;
2) Adding the mixed solution into a reactor for oxidation reaction;
3) Performing gas-liquid separation on the waste alkali liquid after the oxidation reaction by a circulating cooling tower;
4) The liquid phase is discharged to a heat exchanger for cooling through the bottom of the tower;
5) The separated gas phase mixture moves to the upper part of the tower, contacts with the refluxed cold alkali liquor, is condensed and cooled, and the rest gas phase mixture is discharged from the top of the tower;
6) The waste alkali liquid after oxidation is neutralized and then is treated by an evaporation desalting process, so that zero emission of the waste alkali liquid is realized.
In the embodiment, the waste lye mixing in the step 1 comprises the steps of mixing the waste lye with thirty-two percent sodium hydroxide solution, pressurizing by a feed pump, and carrying out oxidation reaction on a ring system entering the space between the inner cylinder and the outer cylinder of the reactor from the upper part of the reactor, wherein when the reaction temperature is not lower than 190 ℃ and the residence time is not lower than 120min, the mass concentration of S2 of effluent water after the waste lye is treated by a wet oxidation process is less than 1mg/L, and the sulfide removal rate is more than 99.99%.
The oxidation reaction in the step 2 comprises that waste alkali liquor enters an annular gap between an inner cylinder and an outer cylinder of the reactor through two symmetrical feed inlets at the upper part of the reactor, compressed air enters the inner cylinder from the bottom of the reactor through a distributor in a bubbling flow mode, high-temperature internal circulation is formed due to different gas contents between the inner cylinder and the outer cylinder and the gas lift effect, the feed waste alkali liquor is preheated in the circulation process, harmful substances are oxidized and decomposed, the oxidation of sodium sulfide in the wet air oxidation process is a two-step series irreversible reaction, firstly, sodium sulfide is oxidized into sodium thiosulfate, and then the sodium thiosulfate is oxidized into sodium sulfate under the alkaline condition.
The gas-liquid separation in the step 3 comprises inner components such as a tray, a feed rectifier and a gas rising pipe, and the like, and the circulating cooling tower is used for condensing and cooling the reacted materials, and the alkaline washing of the tail gas by utilizing the residual alkalinity of the waste alkali liquid after wet oxidation treatment is realized through the design of the internal structure of the washing tower, and then the water washing process is adopted, so that the tail gas can reach the discharge standard.
The reacted material is discharged from the top of the reactor, the material is decompressed and enters a circulating cooling tower, air entering the tower and oxidized waste lye are subjected to gas-liquid separation, the purpose of wet-type air oxidation treatment of the waste lye is to convert sodium sulfide into sodium sulfate as much as possible, according to the chemical reaction kinetics principle, the reaction temperature is increased, the reaction rate of converting sodium sulfide into sodium thiosulfate can be increased, the reaction rate of oxidizing sodium thiosulfate into sodium sulfate can be increased, and therefore the purpose of increasing the sodium sulfate generation rate can be achieved.
The separated gas phase mixture moves to the upper part of the tower and contacts with the back-flowing cold alkali liquor, water vapor and volatile organic compounds in the gas phase mixture are condensed and cooled and return to the bottom of the tower, the rest gas phase mixture is discharged from the top of the tower, the tail gas discharged by the wet oxidation unit comprises excessive air and water vapor, the concentration of hydrogen sulfide in the tail gas accords with the second level standard of GB 14554-1993 malodorous pollutant emission standard through high-altitude discharge (15 m), and the concentration of non-methane total hydrocarbon accords with the requirement of GB 16297-1996 comprehensive emission standard of atmospheric pollutant.
Wherein, the oxidized waste alkali liquor and ninety-eight percent concentrated sulfuric acid are mixed to the neutralization water with pH value of 6 to 9, the zero discharge of the waste alkali liquor can be realized after the treatment of the evaporation desalination process, the sulfur component in the waste water can be fully oxidized into inorganic sulfate radical, the odor is effectively removed, and the Biochemical Oxygen Demand (BOD) and COD value in the waste water are obviously improved after the WAO treatment of the high-concentration organic waste water which is difficult to be biochemically treated, and the waste water can be used as the pretreatment of the biochemical treatment.
Wherein, the heat exchanger is a tubular and horizontal shell-and-tube heat exchanger, the tube side inlet receives oxidized waste lye from the outlet of the circulating cooling tower, the shell side adopts circulating cooling water from public engineering as heat exchange medium, and the temperature of the oxidized waste lye is reduced to below 40 ℃.
The oxidation reaction in the step 2 adopts a wet oxidation reactor, adopts a sleeve type bubbling flow internal circulation reactor, is a vertical reactor with an inner cylinder, waste alkali liquid enters an annular gap between the inner cylinder and the outer cylinder of the reactor through two symmetrical feed inlets at the upper part of the reactor, oxidized tail gas leads a sulfur-making tail gas discharge cylinder to be discharged at high altitude, and treated wastewater is directly discharged to a factory sewage treatment field without impacting a sewage treatment system, so that the problems of subsequent treatment of alkali residues and malodor pollution are thoroughly solved.
Wherein, the liquid phase is discharged to the heat exchanger through the tower bottom, a part of the liquid phase flows back to the middle upper part of the tower after being cooled, and the other part of the liquid phase enters the oxidized waste lye storage tank, and the liquid phase has the characteristics of high treatment efficiency, high reaction speed, small device, wide adaptability, recoverable resources, less secondary pollution and the like, and has been widely applied.
The treatment method of the refined waste lye of the petroleum refining industrial oil product has the beneficial effects that the treatment technology of alkali adding neutralization-wet oxidation-acidification neutralization of the propane dehydrogenation waste lye is developed by combining the water quality characteristics of the waste lye, S2-mass concentration of the effluent of the propane dehydrogenation waste lye is less than 1mg/L after the treatment by the device, COD is less than 200mg/L, malodorous smell of the waste lye is completely removed, the national emission requirement of tail gas of the device is met, the waste lye after oxidation and ninety-eight percent concentrated sulfuric acid are mixed until the neutralization water with pH value of 6 to 9 can be directly treated by an evaporation desalination process, and the zero emission of the waste lye is realized, so that the environmental benefit and the economic benefit are remarkable.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element.
Claims (10)
1. A treatment method of petroleum refining industrial oil product refined waste alkali liquid is characterized in that: the method comprises the following steps:
1) Conveying sodium hydroxide solution and waste alkali liquor through a storage tank for mixing;
2) Adding the mixed solution into a reactor for oxidation reaction;
3) Performing gas-liquid separation on the waste alkali liquid after the oxidation reaction by a circulating cooling tower;
4) The liquid phase is discharged to a heat exchanger for cooling through the bottom of the tower;
5) The separated gas phase mixture moves to the upper part of the tower, contacts with the refluxed cold alkali liquor, is condensed and cooled, and the rest gas phase mixture is discharged from the top of the tower;
6) The waste alkali liquid after oxidation is neutralized and then is treated by an evaporation desalting process, so that zero emission of the waste alkali liquid is realized.
2. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the step 1 of mixing the waste alkali solution comprises the steps of mixing the waste alkali solution with thirty-two percent sodium hydroxide solution, pressurizing by a feed pump, and introducing the mixture into a ring system between an inner cylinder and an outer cylinder of the reactor from the upper part of the reactor to perform oxidation reaction.
3. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the oxidation reaction in the step 2 comprises that waste alkali liquid enters an annular gap between an inner cylinder and an outer cylinder of the reactor through two symmetrical feed inlets at the upper part of the reactor, compressed air enters the inner cylinder from the bottom of the reactor through a distributor in a bubbling flow mode, and high-temperature internal circulation is formed due to different gas contents between the inner cylinder and the outer cylinder and the air lift effect, and the fed waste alkali liquid is preheated in the circulation process, so that harmful substances are oxidatively decomposed.
4. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the gas-liquid separation in the step 3 comprises inner components such as a tray, a feed rectifier, a gas rising pipe and the like, and the circulating cooling tower is used for condensing and cooling the reacted materials and simultaneously carrying out alkaline washing on tail gas by utilizing the residual alkalinity of waste alkali liquid after wet oxidation treatment.
5. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: and discharging the reacted materials from the top of the reactor, decompressing and then entering a circulating cooling tower, and performing gas-liquid separation on air entering the tower and oxidized waste alkali liquor.
6. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the separated gas phase mixture moves to the upper part of the tower and contacts with the back-flowing cold alkali liquor, the water vapor and volatile organic compounds in the gas phase mixture are condensed and cooled, the gas phase mixture returns to the bottom of the tower, and the rest gas phase mixture is discharged from the top of the tower.
7. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the oxidized waste alkali liquor and ninety-eight percent concentrated sulfuric acid are mixed to the neutralized water with the pH value of 6 to 9, and zero emission of the waste alkali liquor can be realized after the waste alkali liquor is directly treated by an evaporation desalting process.
8. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the heat exchanger is a cylindrical and horizontal shell-and-tube heat exchanger, the tube side inlet receives oxidized waste lye from the outlet of the circulating cooling tower, the shell side adopts circulating cooling water from public engineering as a heat exchange medium, and the temperature of the oxidized waste lye is reduced to below 40 ℃.
9. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the oxidation reaction in the step 2 adopts a wet oxidation reactor, adopts a sleeve type bubbling flow internal circulation reactor, is a vertical reactor with an inner cylinder, and waste alkali liquid enters an annular gap between the inner cylinder and the outer cylinder of the reactor through two symmetrical feed inlets at the upper part of the reactor.
10. The method for treating the refined waste alkali liquid of petroleum refining industrial oil products according to claim 1, which is characterized in that: the liquid phase is discharged to a heat exchanger from the bottom of the tower, one part of the cooled liquid phase flows back to the middle upper part of the tower, and the other part of the cooled liquid phase enters a oxidized waste lye storage tank.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311503707.XA CN117550736A (en) | 2023-11-13 | 2023-11-13 | Treatment method of petroleum refining industrial oil product refined waste alkali liquor |
Applications Claiming Priority (1)
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