CN117700039A - Semi-coke wastewater treatment system - Google Patents
Semi-coke wastewater treatment system Download PDFInfo
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- CN117700039A CN117700039A CN202410004441.2A CN202410004441A CN117700039A CN 117700039 A CN117700039 A CN 117700039A CN 202410004441 A CN202410004441 A CN 202410004441A CN 117700039 A CN117700039 A CN 117700039A
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- 239000000571 coke Substances 0.000 title claims abstract description 34
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002351 wastewater Substances 0.000 claims abstract description 77
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 53
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 48
- 238000000605 extraction Methods 0.000 claims abstract description 41
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000011084 recovery Methods 0.000 claims abstract description 28
- 238000004821 distillation Methods 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001704 evaporation Methods 0.000 claims abstract description 21
- 230000008020 evaporation Effects 0.000 claims abstract description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 20
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 20
- 239000004571 lime Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003546 flue gas Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000009993 causticizing Methods 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- 150000002989 phenols Chemical class 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 4
- 230000009615 deamination Effects 0.000 claims abstract description 3
- 238000006481 deamination reaction Methods 0.000 claims abstract description 3
- 230000020477 pH reduction Effects 0.000 claims description 13
- 239000008267 milk Substances 0.000 claims description 10
- 210000004080 milk Anatomy 0.000 claims description 10
- 235000013336 milk Nutrition 0.000 claims description 10
- 239000000428 dust Substances 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 230000029087 digestion Effects 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- -1 fluoride ions Chemical class 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 33
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 239000002585 base Substances 0.000 description 13
- 238000012432 intermediate storage Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 8
- 239000010802 sludge Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001021 Ferroalloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a semi-coke wastewater treatment system, which sequentially and serially comprises an ammonia distillation unit, a boiler, an ammonia water recovery unit and a wastewater treatment unit, wherein the ammonia distillation unit is used for removing ammonia and acid gas in semi-coke wastewater, the acid gas is directly fed into the boiler to be burnt, ammonia water is recovered, and the deaminated wastewater flows downstream; the evaporation concentration unit is used for separating deamination wastewater into condensate and concentrated solution, and the concentrated solution enters the extraction unit; the extraction unit is used for extracting high-concentration phenols and other organic matters from the concentrated solution, recycling the extractant, and stripping the water phase to recover the dissolved extractant and then feeding the extractant into the acid-base recovery unit; and the acid-base recovery unit is used for generating sodium hydroxide solution and carbon dioxide-rich flue gas by a lime causticizing method and a calcium carbonate calcining method, and is added into the system completely. The invention has the beneficial effects that: under the condition of not adding any chemical substances, the semi-coke wastewater is divided into ammonia, oil, phenol and water, and the whole semi-coke wastewater is recycled, so that the whole process is low in investment, reliable in operation, low in operation cost and low in solid waste production.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a semi-coke wastewater treatment system.
Background
The semi-coke is a novel coal conversion product, and has the advantages of high fixed carbon, high specific resistance, high chemical property and the like due to low price, so that the semi-coke is widely applied to industries of calcium carbide, ferroalloy, chemical fertilizer gas making, blast furnace injection, civil clean briquette manufacturing and the like. The coal gas generated by removing volatile matters through low-temperature carbonization in the semi-coke production process is not subjected to high-temperature secondary cracking, so that the semi-coke wastewater contains a large amount of pollutants which are not oxidized at high temperature, and the concentration of the pollutants is far higher than that of coking wastewater.
At present, the main flow of the semi-coke wastewater treatment is as follows: adding a large amount of caustic soda into the semi-coke wastewater, then recovering ammonia by a steam stripping method, adding acid to adjust the pH of the wastewater to be acidic, and recovering phenolic substances in the wastewater by an extraction method, thereby achieving the purpose of recovering ammonia and phenolic substances while reducing the COD value of the wastewater. However, after ammonia distillation and dephenolization, the concentration of COD, ammonia and phenols in the wastewater is still high, and a large amount of acid and alkali are added, so that the mineralization degree of the water phase is doubled, the wastewater is very difficult to treat, the wastewater can not be discharged and recycled up to the standard, and the remaining strong brine has no good treatment method.
The present invention has been made in view of this.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects of the prior art, and providing a semi-coke wastewater treatment system, which is characterized in that an evaporation concentration unit is arranged at the upstream of an extraction unit, semi-coke wastewater is divided into condensate and concentrated solution, the concentration of pollutants such as COD (chemical oxygen demand) in the condensate is very low, the condensate can reach the standard and be discharged after simple biochemical treatment, or the condensate is used for supplementing circulating cooling water, the concentration is only 5-10% of the total water quantity, phenolic substances in the condensate are recovered through the extraction unit, then the phenolic substances in the condensate are recovered through an acid-base recovery unit, and the carbonate alkalinity and sodium ions in the wastewater are used for recovering sodium hydroxide solution and calcium carbonate through causticization reaction, and the calcium carbonate is calcined to recover carbon dioxide, so that the regeneration and recycling of acid-base in the system are realized, the semi-coke wastewater is divided into ammonia, oil, phenol and water under the condition of not adding any chemical substances, the whole process investment is saved, the operation is reliable, the operation cost is low, the solid waste is produced and the solid waste is an ideal solution for the semi-coke wastewater treatment.
In order to solve the technical problems, the invention adopts the basic conception of the technical scheme that: a semi-coke wastewater treatment system sequentially and serially comprises,
the ammonia distillation unit is used for removing ammonia and acid gas in the semi-coke wastewater, directly feeding the acid gas into a boiler for burning, recovering ammonia water, and flowing the deaminated wastewater downstream;
the evaporation concentration unit is used for separating deamination wastewater into condensate and concentrated solution, and the concentrated solution enters the extraction unit;
the extraction unit is used for extracting high-concentration phenols and other organic matters from the concentrated solution, recycling the extractant, and stripping the water phase to recover the dissolved extractant and then feeding the extractant into the acid-base recovery unit;
and the acid-base recovery unit is used for generating sodium hydroxide solution and carbon dioxide-rich flue gas by a lime causticizing method and a calcium carbonate calcining method, and the sodium hydroxide solution and the carbon dioxide-rich flue gas are all recycled.
The sodium hydroxide solution generated by the acid-base recovery unit is added into the wastewater before evaporation and concentration after deacidification and ammonia distillation; the calcium salt generated by the acid-base recovery unit is crystallized, precipitated and dehydrated to form mud cakes, then the mud cakes are calcined to generate calcium oxide and carbon dioxide-rich flue gas, the calcium oxide is used for preparing lime milk, the lime milk is used for causticizing waste water, and the carbon dioxide-rich flue gas is introduced into an acidification tower of the extraction unit after dust removal.
Further, the sodium hydroxide solution generated by the acid-base recovery unit is added into the wastewater before evaporation and concentration after deacidification and ammonia distillation.
Further, calcium salt generated by the acid-base recovery unit is crystallized, precipitated and dehydrated to form mud cakes, and then calcined to generate calcium oxide and flue gas rich in carbon dioxide, wherein the calcium oxide is used for preparing lime milk, and then is used for causticizing wastewater, and the flue gas rich in carbon dioxide is introduced into an acidification tower of the extraction unit after dust removal.
Furthermore, the waste water needs to enter an acidification tower before entering the extraction tower, the waste water is fully contacted with the carbon dioxide-rich flue gas in the acidification tower, and the pH value of the waste water is reduced from alkalinity to weak acidity.
Further, the wastewater treated by the extraction unit is partially diverted to the biochemical treatment unit for reducing the concentration of harmful substances such as chloride ions.
Furthermore, fluoride ions contained in the raw sewage are discharged in the form of calcium fluoride through the deslagging process of the lime digestion device, so that the concentration of the fluoride ions in the system is less than 40mg/l.
Further, a filtering unit is arranged at the upstream of the ammonia distillation unit and is used for filtering and removing solid substances and petroleum in the wastewater.
Furthermore, condensate generated by the evaporation concentration unit enters the biochemical treatment unit, and the biochemical treatment unit is used for treating a small amount of extracted condensate which is split by the condensate and the extraction unit, and is used for supplementing circulating cooling water after treatment.
Compared with the prior art, the invention has the following beneficial effects: under the condition of not adding any chemical substances, the semi-coke wastewater is divided into ammonia, oil, phenol and water, and the whole semi-coke wastewater is recycled, so that the whole process is low in investment, reliable in operation, low in operation cost and low in solid waste production.
Simple process, obvious effect and suitability for popularization and application.
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. It is evident that the drawings in the following description are only examples, from which other drawings can be obtained by a person skilled in the art without the inventive effort. In the drawings:
FIG. 1 is a schematic process flow diagram of a semi-coke wastewater treatment system according to an embodiment of the invention.
In the figure, 1: ammonia distillation unit, 101: pretreatment filter, 102: intermediate tank one, 103: deacidifying ammonia still, 104: an intermediate storage tank II;
2: an evaporation concentration unit; 3: a biochemical treatment unit;
4: extraction unit, 401: intermediate storage tank three, 402: acidification tower, 403: intermediate tank four, 404: extraction column, 405: stripping column, 406: an extractant recovery column;
5: acid-base recovery unit, 501: intermediate tanks five, 502: causticizing crystallization precipitation device, 503: intermediate tanks six, 504: lye filter, 505: recovery lye storage tank, 506: sludge dehydrator, 507: calcination apparatus, 508: lime digestion apparatus, 509: lime milk storage tank.
It should be noted that these drawings and the written description are not intended to limit the scope of the inventive concept in any way, but to illustrate the inventive concept to those skilled in the art by referring to the specific embodiments.
Description of the embodiments
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments will be clearly and completely described with reference to the accompanying drawings in the embodiments of the present invention, and the following embodiments are used to illustrate the present invention, but are not intended to limit the scope of the present invention.
In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
As shown in figure 1, the semi-coke wastewater treatment system comprises an ammonia evaporation unit 1, an evaporation concentration unit 2, a biochemical treatment unit 3, an extraction unit 4 and an acid-base recovery unit 5 which are sequentially connected in series.
In the embodiment of the invention, the ammonia distillation unit 1 is used for removing ammonia and acid gas in semi-coke wastewater, the acid gas is directly connected to a boiler for burning, ammonia water can be recovered, and the rest wastewater flows to a downstream unit. The front end of the ammonia still unit 1 is provided with a pretreatment filter 101 for removing suspended matters with the diameter larger than 5 micrometers in wastewater, and preventing the deacidification ammonia still tower 103 and the subsequent processes from being blocked. The first intermediate storage tank 102 is arranged between the pretreatment filter 101 and the deacidification ammonia distillation tower 103 and is used for temporarily storing wastewater and adjusting water quantity. The second intermediate storage tank 104 is arranged behind the deacidification ammonia distillation tower 103 and is used for temporarily storing the wastewater after deacidification and ammonia removal, the second intermediate storage tank 104 is provided with a PH value detection device, and the added alkali liquid amount is adjusted according to the detected PH value.
And alkaline liquor is added into the second intermediate storage tank 104, the pH value of the wastewater is adjusted to be alkaline, phenolic substances in the wastewater exist in the form of phenolic sodium salt, and most of phenolic substances are reserved in the concentrated solution in the subsequent evaporation and concentration process, so that the concentration of organic substances in condensate liquid generated in the evaporation process is very low, and the biochemical treatment is easy.
In the embodiment of the present invention, the evaporation and concentration unit 2 is an evaporator, specifically, a multi-effect evaporator or an MVR evaporator. By introducing steam into the deacidification ammonia removal wastewater in the evaporator, the liquid water is continuously evaporated, phenolic substances in the wastewater are reserved in the concentrated solution in the process, the concentration of the phenolic substances is greatly increased to 10-20 times of that of the original wastewater, and the extraction of the phenolic substances is easier.
In the embodiment of the invention, the biochemical treatment unit 3 is used for treating condensate generated by the evaporation concentration unit 2, the COD value of the condensate is lower than 1000mg/L, the COD value of the part of wastewater can be reduced to be lower than 50 mg/L only by simple biochemical treatment, and the wastewater can be directly used as make-up water of circulating cooling water after the treatment is completed.
In the embodiment of the invention, the concentrated solution generated by the evaporation and concentration unit 2 is conveyed to the extraction unit 4, and the front end of the extraction unit 4 is provided with a third intermediate storage tank 401 for temporarily storing the alkaline concentrated solution.
After the acidification tower 402 is arranged in the intermediate storage tank III 401, concentrated solution is introduced into the top of the acidification tower 402, carbon dioxide-rich flue gas is introduced into the bottom of the acidification tower 402, and after the concentrated solution and the flue gas are fully contacted in the opposite flow in the tower, CO 2 The phenol sodium salt is dissolved in the concentrated solution and reacts with the phenol sodium salt to convert the phenol sodium salt into phenol, the PH of the concentrated solution is gradually reduced to about 5.5, and a middle storage tank IV 403 arranged behind the acidification tower 402 is used for temporarily storing the weak acid phenol-containing wastewater.
The extraction unit 4 further comprises an extraction column 404, a stripping column 405 and an extractant recovery column 406. The oil phase extracted from extraction column 404 and fed to extractant recovery column 406 is referred to as dirty extractant, the oil phase extracted from extractant recovery column 406 and fed back to extraction column 404 is referred to as clean extractant.
Phenolic wastewater enters from the top of the extraction tower 404, and extractant is introduced from the bottom of the extraction tower 404. After the phenol-containing wastewater and the extractant are sufficiently contacted in the column in a counter-current manner, the extractant which dissolves most of the phenol substances in the wastewater rises to the upper part of the extraction column 404, becomes a dirty extractant, and the wastewater containing a small amount of extractant flows to the lower part of the extraction column 404.
The top of the stripping tower 405 receives the wastewater extracted from the lower part of the extraction tower 404, fresh water vapor is introduced into the bottom of the stripping tower 405, after the wastewater and the steam flow in opposite directions in the stripping tower 405 and fully contact, the steam containing the extractant is extracted from the upper part of the stripping tower 405, the wastewater is extracted from the lower part of the stripping tower 405, and the extracted wastewater is cooled and then sent to a subsequent unit for treatment.
The top of the extractant recovery column 406 receives the dirty extractant extracted from the upper portion of the extraction column 404, and the bottom of the extractant recovery column 406 receives two types of steam, namely, the steam containing extractant extracted from the upper portion of the stripping column 405 and the fresh steam. After the liquid and the steam are fully contacted in the opposite flow way in the extractant recovery tower 406, the upper layer of the net extractant is returned to the extraction tower 404 for continuous use; the lower phenol-containing solution can be directly sold after being extracted.
Through the arrangement, the semi-coke wastewater is pretreated, deacidified, deaminated and adjusted in pH value in the ammonia distillation unit 1, so that the treatment of the evaporation concentration unit 2 is facilitated. In the evaporation and concentration unit 2, on the one hand, a concentrate with a high concentration of phenolic substances is obtained, and on the other hand, a condensate which is easy to handle by the biochemical treatment unit 3 is obtained. Wherein the resulting concentrate reduces the amount of waste water fed to the extraction unit 4 and reduces the amount of extractant used in the extraction unit 4.
In the embodiment of the invention, the front end of the acid-base recovery unit 5 is provided with a fifth intermediate storage tank 501 for temporarily storing the wastewater treated by the extraction unit 4. The extracted wastewater contains chloride ions, sulfate ions and other unknown substances, and as the chloride ions and other harmful substances are continuously accumulated due to the water circulation in the system, 10% -30% of the wastewater needs to be split into the biochemical treatment unit 3 in order to avoid corrosion or scaling of equipment and pipelines, and the rest 70% -90% of the wastewater is sent to subsequent equipment for continuous treatment.
After the causticizing crystallization precipitation device 502 is arranged in the intermediate storage tank five 501, in the causticizing crystallization precipitation device 502, naCO in the wastewater 3 With Ca (OH) in milk of lime 2 Reacting to generate NaOH and CaCO 3 The sediment produced by the causticizing crystallization precipitation device 502 after precipitation is sent to a sludge dehydrator 506, and the filtrate containing NaOH produced by the sediment is sent to a middle storage tank six 503.
The sludge dehydrator 506 dehydrates and separates the bottom sludge into filtrate and sludge cake with lower water content, the filtrate is sent to the intermediate storage tank six 503, and the sludge cake is discharged at the slag discharge port of the sludge dehydrator 506.
The main component in the mud cake is CaCO 3 At the same time contain a small amount of CaSO 4 And CaF 2 。
The acid-base recovery unit 5 further comprises a calcination device 507, a lime digestion device 508 and a dust remover 510.
Delivering mud cakes generated by the sludge dehydrator 506 into a calcining device 507, controlling the calcining temperature of the calcining device 507 to be less than 1000 ℃ and controlling the calcining temperature of CaCO to be less than 1000% 3 Decomposing to form CaO and CO 2 The calcined solids are fed to lime digestion device 508 and the resulting fumes are fed to dust separator 510.
In the lime digestion apparatus 508, caO in the solid matter reacts with water transported by the intermediate storage tank six 503 to form a lime milk solution, and the lime milk solution is calcined to form undissolved CaSO 4 And CaF 2 Is discharged from the system through slag discharge.
The dust remover 510 receives the dust-containing gas generated by the calcining device 507, and the solid matters are collected and then transported to the outside for treatment, and the dust is removed and mainly contains CO 2 Is returned to the acidification tower 402 in the extraction unit 4 for use.
In addition to this, the acid-base recovery unit 5 comprises a lime milk tank 509, an alkali liquor filter 504 and a recovery alkali liquor tank 505.
A lime milk tank 509 is provided after the lime digestion device 508 for storing lime milk solution while receiving NaOH-containing solution from the intermediate tank six 503.
The lye filter 504 is used to filter the solution extracted in the intermediate tank six 503.
The recycle lye reservoir 505 is used to temporarily store the solution that is delivered to the ammonia distillation unit 1.
By the arrangement, most F in the semi-coke wastewater is removed - And tightly control F in system - The concentration is less than 40mg/L, ensuring F - Without corroding equipment and piping in the system. Meanwhile, substances such as calcium carbonate and the like generated in the wastewater treatment process are fully utilized, the use amount of fresh tap water is reduced, and the running cost of the system is reduced.
Examples
In the embodiment of the invention, the raw water volume is 6 m 3 And (h), after oil separation and filtration, directly entering an ammonia distillation unit 1, wherein the steam pressure used by the ammonia distillation unit 1 is about 1.0MPa, and the steam temperature is about 185 ℃; condensing the ammonia-containing steam laterally extracted from the ammonia still to obtain ammonia water with ammonia concentration of about 15%The top is discharged and contains acid gases such as carbon dioxide, hydrogen sulfide and the like, the wastewater after ammonia distillation is added with sodium hydroxide solution, the PH value of the wastewater entering a concentration unit is controlled to be 11-12, and the water quality conditions of the wastewater after units such as deacidification ammonia distillation, evaporation concentration, extraction, biochemical treatment and the like are shown in the following table.
| Species of type | Water quantity (m) 3 /h） | pH | H 2 S or sulfide (mg/l) | Oils (mg/l) | NH 3 （mg/l） | Phenol (mg/l) | COD（mg/l） |
| Raw water | 6 | 8~9 | 189~820 | 577.9~720 | 3500~6500 | 6428~8000 | 35000~55000 |
| Water after deacidification and ammonia distillation | 6 | 8~9 | 10~20 | 400~500 | 150~300 | 6300~7800 | 33130~52407 |
| Concentrated solution | 0.6 | \ | \ | 3800~5000 | 1200~3100 | 56000~75000 | \ |
| Extracting the concentrated solution | 0.6 | \ | \ | 650~710 | 980~2420 | 345~450 | 5600~7300 |
| Condensate liquid | 5.4 | \ | \ | 20~40 | 13~21 | 20~41 | 580~1420 |
| After the condensate is biochemically treated | 5.3 | 6.5~7.5 | \ | < 0.5 | < 2.0 | < 0.3 | < 50 |
The condensate has a salt content of less than 100mg/l, is the make-up water of circulating cooling water with very good quality, and can be fully recycled.
Examples
In the embodiment of the invention, the raw water volume is 100m 3 And (h) after oil removal and filtration, directly entering an ammonia distillation unit 1, wherein the steam pressure used by the ammonia distillation unit 1 is 0.4-0.5MPa, and the steam temperature is 145-155 ℃; the ammonia-containing steam laterally extracted from the ammonia distillation tower is condensed to obtain ammonia water with ammonia concentration of about 15%, acid gas containing carbon dioxide, hydrogen sulfide and the like is discharged from the top, sodium hydroxide solution is added into the wastewater after ammonia distillation, ph value of the wastewater flowing into a concentration unit is controlled to be 11-12, and water quality conditions of the wastewater after units such as deacidification ammonia distillation, evaporation concentration, extraction, biochemical treatment and the like are shown in the table below.
| Species of type | Water quantity (m) 3 /h） | pH | H 2 S orSulfide (mg/l) | Oils (mg/l) | NH 3 （mg/l） | Phenol (mg/l) | COD（mg/l） |
| Raw water | 100 | 8.5~9.0 | 1089~1220 | 6779~7920 | 3071~5943 | 7128~12140 | 38158~57430 |
| Water after deacidification and ammonia distillation | 100 | 8.5~9.0 | 19~39 | 582~703 | 242~397 | 6621~10859 | 34109~52674 |
| Concentrated solution | 10 | \ | \ | 4095~5211 | 1177~3352 | 58347~73610 | \ |
| Extracting the concentrated solution | 6.9 | \ | \ | 589~727 | 1060~2322 | 345~450 | 5636~7550 |
| Condensate liquid | 96 | \ | \ | 23~38 | 14~27 | 23~51 | 544~1497 |
| After the condensate is biochemically treated | 91 | 6.2~7.1 | \ | < 0.5 | < 2.0 | < 0.3 | < 50 |
The foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited to the above-mentioned embodiment, but is not limited to the above-mentioned embodiment, and any simple modification, equivalent change and modification made by the technical matter of the present invention can be further combined or replaced by equivalent embodiments within the scope of the technical proposal of the present invention without departing from the scope of the technical proposal of the present invention.
Claims (7)
1. A semi-coke wastewater treatment system is characterized by comprising, in series,
the ammonia distillation unit is used for removing ammonia and acid gas in the semi-coke wastewater, directly feeding the acid gas into a boiler for burning, recovering ammonia water, and flowing the deaminated wastewater downstream;
the evaporation concentration unit is used for separating deamination wastewater into condensate and concentrated solution, and the concentrated solution enters the extraction unit;
the extraction unit is used for extracting high-concentration phenols and other organic matters from the concentrated solution, recycling the extractant, and stripping the water phase to recover the dissolved extractant and then feeding the extractant into the acid-base recovery unit;
and the acid-base recovery unit is used for generating sodium hydroxide solution and carbon dioxide-rich flue gas by a lime causticizing method and a calcium carbonate calcining method, and the sodium hydroxide solution and the carbon dioxide-rich flue gas are all recycled.
2. A semi-coke wastewater treatment system according to claim 1, wherein,
the sodium hydroxide solution generated by the acid-base recovery unit is added into the wastewater before evaporation and concentration after deacidification and ammonia distillation; the calcium salt generated by the acid-base recovery unit is crystallized, precipitated and dehydrated to form mud cakes, and then calcined to generate calcium oxide and flue gas rich in carbon dioxide, wherein the calcium oxide is used for preparing lime milk and is used for causticizing wastewater; the flue gas rich in carbon dioxide is introduced into an acidification tower of an extraction unit after dust removal.
3. A semi-coke wastewater treatment system according to claim 1 and 2, wherein the wastewater is fed into an acidification tower before being fed into the extraction tower, and wherein the wastewater is fully contacted with carbon dioxide-rich flue gas in the acidification tower, and wherein the PH of the wastewater is reduced from alkaline to slightly acidic.
4. The semi-coke wastewater treatment system according to claim 1 or 2, wherein a part of the wastewater treated by the extraction unit is diverted to the biochemical treatment unit for reducing the concentration of harmful substances such as chloride ions.
5. A semi-coke wastewater treatment system according to claim 1 and claim 2, wherein the lime digestion device discharges slag to remove fluoride ions contained in raw wastewater in the form of calcium fluoride, thereby resulting in a fluoride ion concentration of less than 40mg/l in the system.
6. A semi-coke wastewater treatment system according to claim 1 and 2, wherein a filtering unit is arranged at the upstream of the ammonia distillation unit for filtering and removing solid substances and petroleum substances in the wastewater.
7. The semi-coke wastewater treatment system according to claim 1, wherein condensate generated by the evaporation concentration unit enters the biochemical treatment unit, and the biochemical treatment unit is used for treating a small amount of extracted concentrated solution split by the condensate and the extraction unit, and the treated concentrated solution is used for supplementing circulating cooling water.
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| CN202410004441.2A CN117700039A (en) | 2024-01-03 | 2024-01-03 | Semi-coke wastewater treatment system |
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