CN118812107B - High-difficulty degradation-resistant salt-containing wastewater treatment equipment and technology - Google Patents
High-difficulty degradation-resistant salt-containing wastewater treatment equipment and technology Download PDFInfo
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- 239000000945 filler Substances 0.000 claims abstract description 146
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000002351 wastewater Substances 0.000 claims abstract description 96
- 238000001179 sorption measurement Methods 0.000 claims abstract description 68
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- 238000004065 wastewater treatment Methods 0.000 claims abstract description 20
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- 239000012528 membrane Substances 0.000 claims description 5
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000008394 flocculating agent Substances 0.000 claims description 4
- 238000000108 ultra-filtration Methods 0.000 claims description 4
- 238000011221 initial treatment Methods 0.000 claims description 3
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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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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)
- Water Treatment By Sorption (AREA)
Abstract
本发明公开了一种高难度难降解含盐废水处理设备及工艺，属于含盐废水处理技术领域；包括粗杂质过滤单元、絮凝单元、絮凝物过滤单元、臭氧催化氧化单元、复合填料处理单元以及蒸发单元；复合填料处理单元内呈上下分布有第一层填料和第二层填料，第一层填料为大孔吸附树脂；第二层填料由改性活性炭、改性壳聚糖和改性氧化石墨烯‑碳纤维组成；第一层填料和第二层填料组成复合填料；改性活性炭为铜基活性炭；改性壳聚糖由壳聚糖先经二氧化硅改性，再接枝聚乙烯醇所得；改性氧化石墨烯‑碳纤维由氧化石墨烯‑碳纤维接枝聚乙烯醇所得；经该设备处理后，含盐废水的COD含量低于10mg/L，TDS≤100mg/L。
The invention discloses a highly difficult and refractory salt-containing wastewater treatment equipment and process, belonging to the technical field of salt-containing wastewater treatment; the equipment comprises a coarse impurity filtering unit, a flocculation unit, a flocculent filtering unit, an ozone catalytic oxidation unit, a composite filler processing unit and an evaporation unit; a first layer of filler and a second layer of filler are arranged in an upper and lower manner in the composite filler processing unit, the first layer of filler is a macroporous adsorption resin; the second layer of filler is composed of modified activated carbon, modified chitosan and modified graphene oxide-carbon fiber; the first layer of filler and the second layer of filler form a composite filler; the modified activated carbon is copper-based activated carbon; the modified chitosan is obtained by first modifying chitosan with silicon dioxide and then grafting polyvinyl alcohol; the modified graphene oxide-carbon fiber is obtained by grafting graphene oxide-carbon fiber with polyvinyl alcohol; after being treated by the equipment, the COD content of the salt-containing wastewater is lower than 10 mg/L, and the TDS is less than or equal to 100 mg/L.
Description
Technical Field
The invention relates to the technical field of salt-containing wastewater treatment, in particular to high-difficulty degradation-resistant salt-containing wastewater treatment equipment and technology.
Background
High-salt wastewater refers to wastewater with a Total Dissolved Solids (TDS) mass fraction of greater than or equal to 1%, which is typically derived from industrial wastewater in the fields of petroleum processing, coal chemical industry, printing and dyeing, paper making, and the like, and concentrate after treatment by membrane or electrodialysis equipment. The high-salt wastewater has complex components, contains a large amount of inorganic salts (such as chloride ions, sodium ions, sulfate ions and the like) and also contains a large amount of organic pollutants (such as benzene, phenol, polycyclic aromatic hydrocarbon and the like) which are difficult to degrade. If the high-salinity wastewater is directly discharged, the high-salinity wastewater not only can cause great harm to water organisms, but also can cause environmental problems such as salinization of soil and the like, and has great negative influence on social and economic development.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide high-difficulty degradation-resistant salt-containing wastewater treatment equipment and process, so as to at least achieve the aim of effectively reducing TDS and COD in wastewater.
The technical purpose of the invention is realized by the following technical scheme:
the high-difficulty degradation-resistant salt-containing wastewater treatment equipment comprises a coarse impurity filtering unit, a flocculation unit, a flocculate filtering unit, an ozone catalytic oxidation unit, a composite filler treatment unit and an evaporation unit;
Wherein, a first layer of filler and a second layer of filler are distributed in the composite filler treatment unit up and down, and the first layer of filler is macroporous adsorption resin; the second layer of filler consists of modified activated carbon, modified chitosan and modified graphene oxide-carbon fiber; the first layer of filler and the second layer of filler form a composite filler;
wherein the modified activated carbon is copper-based activated carbon;
the modified chitosan is obtained by modifying chitosan by silicon dioxide and then grafting polyvinyl alcohol;
The modified graphene oxide-carbon fiber is obtained by grafting graphene oxide-carbon fiber with polyvinyl alcohol.
As some embodiments of the application, the flocculating agent adopted by the flocculating unit is polyaluminum sulfate, and the flocculating aid is carboxymethyl chitosan grafted with acrylamide.
As some embodiments of the application, the floc filtration unit comprises a filtration tank loaded with activated zeolite, a multi-media filter connected to the water outlet end of the filtration tank, and an ultrafiltration membrane connected to the water outlet end of the multi-media filter.
In some embodiments of the present application, in the ozone catalytic oxidation unit, the catalyst is activated carbon loaded with copper-manganese oxide.
As some embodiments of the present application, in the composite filler treatment unit, the mass ratio between the first layer of filler and the second layer of filler is 1:3-3.5.
As some embodiments of the present application, the second filler layer comprises the following components in parts by weight:
70-85 parts of modified activated carbon, 10-20 parts of modified chitosan and 5-13 parts of modified graphene oxide-carbon fiber.
As some embodiments of the present application, the second filler layer comprises the following components in parts by weight:
75-83 parts of modified activated carbon, 12-18 parts of modified chitosan and 8-11 parts of modified graphene oxide-carbon fiber.
As some embodiments of the present application, the second filler layer comprises the following components in parts by weight:
80 parts of modified activated carbon, 16 parts of modified chitosan and 10 parts of modified graphene oxide-carbon fiber.
As some embodiments of the present application, the composite packing treatment unit includes an adsorption tower, and two placement barrels disposed in the adsorption tower in an overlapping manner; the placing barrel comprises a supporting filter plate and a coaming plate arranged around the supporting filter plate;
the two placing barrels are respectively connected with the inner wall of the adsorption tower in a sliding manner;
The top walls of the two placing barrels are provided with two handles, and the bottom wall of the placing barrel above is provided with a first slot for inserting the handle below; the adsorption tower roof is provided with the second slot that is used for inserting and establishes the top handle.
In addition, in order to achieve the purpose, the application also provides a treatment process of the high-difficulty and difficult-degradation salt-containing wastewater, which adopts the treatment equipment to treat the wastewater, and comprises the following steps:
s1, introducing high-difficulty nondegradable salt-containing wastewater to be treated into a coarse impurity filtering unit, and removing dregs in the wastewater to obtain wastewater subjected to primary treatment;
s2, introducing the wastewater subjected to the first treatment into a flocculation unit, sequentially adding a flocculant and a flocculation aid in the flocculation process, and obtaining wastewater subjected to the second treatment after flocculation treatment;
S3, introducing the wastewater subjected to the second treatment into a flocculate filtering unit to obtain wastewater subjected to the third treatment;
S4, introducing ozone into the wastewater subjected to the third treatment for catalytic oxidation treatment to obtain wastewater subjected to the fourth treatment;
s5, carrying out primary desalination and organic adsorption treatment on the fourth treated wastewater through a composite filler treatment unit to obtain fifth treated wastewater;
and S6, evaporating the wastewater from the fifth treatment to obtain wastewater from the sixth treatment.
Compared with the prior art, the invention has the beneficial effects that:
1. The application can desalt and remove organic matters from the high-difficulty and difficult-degradation salt-containing wastewater by arranging the high-difficulty and difficult-degradation salt-containing wastewater treatment equipment comprising the coarse impurity filtering unit, the flocculation unit, the flocculate filtering unit, the ozone catalytic oxidation treatment unit, the composite filler treatment unit and the evaporation unit, and after the treatment, the COD content of the water is lower than 10mg/L, and the TDS is less than or equal to 100mg/L, thereby meeting the emission standard.
2. The application defines a composite filler treatment unit to comprise a first layer of filler and a second layer of filler, wherein the first layer of filler is macroporous adsorption resin, the second layer of filler consists of modified activated carbon, modified chitosan and modified graphene oxide-carbon fiber, and the first layer of filler can adsorb part of organic matters in wastewater and remove part of salt, so that the influence of the salt on the capability of adsorbing the organic matters of the second layer of filler is reduced, and the removal rate of the organic matters treated by the ozone catalytic oxidation treatment unit can reach 99% through the synergistic effect of the two fillers; in addition, the compounding of the three fillers in the second layer of fillers not only has a good organic matter adsorption effect in the primary operation, but also has a good adsorption effect after 300 hours of accumulated operation, and the service life of the composite filler is effectively prolonged.
Drawings
Fig. 1: the structure schematic diagram of the salt-containing wastewater treatment equipment in the application;
fig. 2: a schematic structural diagram of the front view direction of the composite filler treatment unit;
Fig. 3: FIG. 2 is a schematic top view of the placement barrel;
in the figure: 1-adsorption tower, 2-placing barrel, 201-supporting filter plate, 202-coaming, 3-handle and 4-second slot.
Detailed Description
The high-difficulty degradation-resistant salt-containing wastewater treatment equipment comprises a coarse impurity filtering unit, a flocculation unit, a flocculate filtering unit, an ozone catalytic oxidation unit, a composite filler treatment unit and an evaporation unit;
Wherein, a first layer of filler and a second layer of filler are distributed in the composite filler treatment unit up and down, and the first layer of filler is macroporous adsorption resin; the second layer of filler consists of modified activated carbon, modified chitosan and modified graphene oxide-carbon fiber; the first layer of filler and the second layer of filler form a composite filler;
The modified activated carbon is copper-based activated carbon, and the specific preparation method comprises the following steps: 5g of 50-100 mesh active carbon is selected, 40 mL CuCl 2 solution with the concentration of 0.5 mol.L -1 is added, stirring is carried out for 8 hours at the stirring speed of 150r/min at normal temperature, then water is taken out for washing to be neutral, the active carbon is dried at 100-105 ℃ for 24 h, and then the active carbon is calcined at 500 ℃ for 2h under the atmosphere of N 2, thus obtaining the modified active carbon.
The modified chitosan is obtained by modifying chitosan by silicon dioxide and then grafting polyvinyl alcohol; the specific preparation method of the modified chitosan comprises the following steps:
S1, adding 5g of nano silicon dioxide into 210g of acetone, adjusting the pH to 2-2.5, adding 20g of epichlorohydrin at normal temperature, stirring at 45-50 ℃ for 10 hours at 200-250r/min, and removing the acetone and the epichlorohydrin after stirring;
S2, adding 8g of chitosan into 190g of isopropanol, adding 2g of sodium hydroxide, adding the reactant obtained in the step S1 at normal temperature, stirring for 10 hours at 200-250r/min, filtering after stirring, washing, and drying in vacuum to obtain a solid initial product;
S3, 150g of N, N-dimethylformamide, 10g of solid initial product, 100g of polyvinyl alcohol and 1.5 toluene diisocyanate are taken and added into a reaction bottle to react for 10 hours at 50 ℃, and after the reaction is finished, the modified chitosan is obtained by filtering, washing and drying;
The modified graphene oxide-carbon fiber is obtained by grafting graphene oxide-carbon fiber with polyvinyl alcohol; the preparation method of the modified graphene oxide-carbon fiber comprises the following steps:
S1, preparing graphene oxide-carbon fiber by adopting a method of experimental example I in a patent CN 201210268226.0;
S2, 180g of N, N-dimethylformamide, 6g of graphene oxide-carbon fiber, 100g of polyvinyl alcohol and 1.5 toluene diisocyanate are taken and added into a reaction bottle, and the reaction is carried out for 10 hours at 50 ℃, and then the modified graphene oxide-carbon fiber is obtained after filtration, washing and drying.
In the application, the coarse and fine gratings are arranged in the coarse impurity filtering unit, so that dregs in the high-difficulty and difficult-to-degrade salt-containing wastewater can be removed;
adding a flocculating agent and a flocculating aid into the flocculating unit to flocculate the wastewater to the greatest extent;
the flocculate filtering unit can remove flocculate;
the ozone catalytic oxidation treatment unit can primarily remove organic matters in the wastewater;
the first layer of filler in the composite filler treatment unit can be used for carrying out preliminary desalination on the wastewater and removing a little organic matters, and the second layer of filler can be used for carrying out deep removal on the organic matters in the wastewater;
the evaporation unit can deeply remove salts in the wastewater.
After the treatment by the equipment, the COD content in the treated water is lower than 10mg/L, the first class A water outlet standard is met, and the TDS is less than or equal to 100mg/L.
In addition, the development thought of the composite filler treatment unit in the application is as follows:
Ozone reacts very slowly with some organic contaminants (e.g., saturated aromatic hydrocarbons), while some intermediates such as aldehydes, carboxylic acids, etc. do not continue to react with ozone, and therefore have limited removal of organics; based on the method, modified activated carbon and modified chitosan are added into the composite filler treatment unit, the specific surface area and the pore diameter of the modified activated carbon are larger than those of common activated carbon, and part of oxygen-containing functional groups of the activated carbon are covered by copper base, so that more active adsorption points can be provided, the attraction to hydrophobic organic matters is increased, pi-complex bonds can be formed with phenyl groups in saturated aromatic hydrocarbon, the affinity to the surface of saturated aromatic hydrocarbon such as toluene is obviously improved, and therefore, the modified activated carbon can obviously improve the adsorption effect to organic matters, particularly aldehydes and saturated aromatic hydrocarbon organic matters, so as to further reduce COD.
Compared with chitosan, the modified chitosan has a reticular structure after being modified by silicon dioxide, the mechanical strength of the modified chitosan is obviously improved, and the technical defect that the adsorption effect is reduced due to the fact that the structure of single chitosan is easily damaged under the long-time adsorption effect due to poor mechanical property and easy brittleness is obviously overcome; meanwhile, the high temperature resistance of the modified chitosan can be obviously improved, and the technical defect that the integral structure of the composite filler is damaged due to the decomposition of the chitosan structure in the regeneration process, so that the adsorption effect is reduced or the adsorption capacity is invalid due to the fact that the high temperature resistance of single chitosan is poor can be obviously overcome. In addition, as the modified chitosan has a hole structure, compared with single chitosan, the physical adsorption effect on organic matters can be remarkably improved; and then, on the basis of modifying silicon dioxide, polyvinyl alcohol is grafted, a polyacrylic acid molecular chain can be introduced into a modified chitosan matrix to form a three-dimensional network structure with a more stable structure, when the three-dimensional network structure is subjected to water pressure, a chemical crosslinking network can buffer partial pressure, so that the compression resistance of the modified chitosan is improved, the structural stability of the modified chitosan is further improved, and meanwhile, the chitosan grafted polyacrylic acid contains rich hydroxyl, amino and carboxyl hydrophilic groups, so that the adsorption effect on hydrophilic organic matters such as acid organic matters and the adsorption effect on heavy metal ions can be remarkably improved. In addition, the modified chitosan has stronger removal capability for heavy metals such as pb, cr, cu, zn. The modified chitosan has a strong adsorption effect on organic matters, particularly hydrophilic organic matters, and the adsorption effect on the organic matters can be remarkably improved through the synergistic effect of the modified chitosan and the modified activated carbon.
In addition, because the modified activated carbon and the modified chitosan are in hard contact, the surfaces of the modified activated carbon and the modified chitosan are worn and broken due to extrusion and the like under the action of long-time water pressure, so that the surface structure of the modified activated carbon and the surface groups are seriously influenced, the adsorption performance of the composite filler is influenced, and on the basis, the graphene oxide is added, so that the lubricity and the overall wear resistance between the components of the composite filler can be obviously improved, and the wear or pressure loss degree between the modified activated carbon and the modified chitosan is further reduced; in addition, the oxygen-containing functional groups contained in the modified chitosan can form hydrogen bonds with the modified chitosan and a little oxygen-containing functional groups on the surface of the modified activated carbon, so that the bonding degree between the modified chitosan and other fillers is effectively improved.
However, in the long-time adsorption process, graphene oxide is moved to a certain extent due to the action of water flow, so that uneven distribution of composite filler is caused, and on the basis of the method, graphene oxide is replaced by composite material graphene oxide-carbon fiber, fibers in the graphene oxide-carbon fiber can penetrate through the whole composite filler, meanwhile, hydrogen bonds and the like can be formed between the graphene oxide-carbon fiber, chitosan and activated carbon, so that the binding force between fillers is improved, and graphene oxide can be stably and uniformly distributed in the whole filler system, and even under the impact of water flow, the migration of graphene oxide can be effectively avoided due to the strong binding action between the graphene oxide and the carbon fiber, so that the uniformity of the filler system is ensured. Meanwhile, due to the fact that graphene oxide-carbon fibers are filled between the fillers, hard contact between the fillers can be effectively overcome, the extrusion damage degree between the fillers is effectively reduced, and the problems that active carbon structure is damaged, holes are blocked and the adsorption performance is seriously affected due to long-time water flow impact are effectively overcome.
However, due to the poor mechanical strength of the fiber in the graphene oxide-carbon fiber, the fiber can collapse and compress under the long-time adsorption effect, the hole structure is influenced, the adsorption effect is obviously reduced, and the wastewater flux is influenced, based on the modified graphene oxide-carbon fiber, the polyvinyl alcohol is grafted, the graphene oxide-carbon fiber can be formed by taking the graphene oxide and the carbon fiber as crosslinking centers, and a complex three-dimensional chemical crosslinking interpenetrating network is formed with the polyvinyl alcohol, so that when the modified graphene oxide and the carbon fiber are subjected to extrusion force of water pressure and other fillers, the chemical crosslinking interpenetrating network can buffer local stress, further improve strain resistance of the modified graphene oxide-carbon fiber, and reduce collapse and compression degrees of the modified graphene oxide-carbon fiber.
Through the synergistic effect of the components, the removal rate of the residual organic matters after being treated by the ozone catalytic oxidation unit can reach about 90 percent. However, the wastewater treated in the invention is high-salt wastewater, and the adsorption efficiency of the composite filler is reduced due to the fact that a large amount of inorganic salt is contained in the wastewater, and on the basis of the wastewater, in order to further improve the removal capacity of the composite filler treatment unit on organic matters, D3520 macroporous adsorption resin is added, so that the organic matters can be adsorbed through the macroporous resin, preliminary desalination can be realized, the influence of salt on the composite filler is reduced to the greatest extent, the adsorption performance of other fillers on the organic matters is improved, and the removal rate of the organic matters can reach about 99% after the macroporous resin treatment is tested.
In order to further improve the flocculation effect, as some possible embodiments of the present application, a flocculant and a flocculation aid of the flocculation unit are further limited, that is, the flocculant adopted by the flocculation unit is polyaluminum sulfate, the flocculation aid is carboxymethyl chitosan grafted with acrylamide, and the preparation method refers to the patent with application number CN 201010223727.8.
In the scheme, firstly, polyaluminium sulfate is added to perform compression electric double layer destabilization, and then, carboxymethyl chitosan of acrylamide is added to realize bridging effect, so that fine and loose floccules become coarse and dense, and further, the flocculation effect is remarkably improved.
Wherein the adding amount of the polyaluminum sulfate is 10-50 mg/L, and the adding amount of the carboxymethyl chitosan grafted with the acrylamide is 0.1-0.5mg/L. In the scheme, compared with the direct use of polyacrylamide series organic synthetic polymeric flocculant, the carboxymethyl chitosan grafted with the acrylamide is adopted, so that the cost can be remarkably saved, and the flocculation effect is better.
In order to further enhance the removal effect of the flocs, as some possible embodiments of the present application, the floc filtering unit is further defined as comprising a filtering tank loaded with 10-30 mesh activated zeolite, a multi-medium filter connected to the water outlet end of the filtering tank, and an ultrafiltration membrane connected to the water outlet end of the multi-medium filter. In this scheme, through limiting the flocculation thing filter unit, can effectively improve the removal effect of flocculation thing.
In order to further improve the removal effect of the organic matters, as some possible embodiments of the present application, a catalyst in the ozone catalytic oxidation unit is further limited, that is, in the ozone catalytic oxidation unit, activated carbon loaded with copper-manganese oxide is used as the catalyst. The catalyst preparation method in this embodiment can be referred to as example 1 in the patent of patent application CN 202210283032.1. In the scheme, the catalyst can improve the organic matter removal rate in the ozone catalytic oxidation unit by at least 15% compared with the conventional catalyst manganese dioxide by limiting the types of the catalyst.
In addition, copper and manganese particles in the activated carbon can be gradually leached into water in a long-time adsorption process, and the leached copper and manganese ions can be adsorbed by the modified chitosan, so that heavy metal content in the wastewater is prevented from being aggravated.
In order to further improve the organic matter removal effect, as some possible embodiments of the present application, the mass ratio of the first layer of filler to the second layer of filler is further defined, that is, in the composite filler treatment unit, the mass ratio between the first layer of filler and the second layer of filler is 1:3-3.5.
In order to further improve the removal effect of the organic matters, as some possible embodiments of the present application, the amount of each component in the second layer of filler is further limited, that is, the weight parts of each component in the second layer of filler are as follows:
70-85 parts of modified activated carbon, 10-20 parts of modified chitosan and 5-13 parts of modified graphene oxide-carbon fiber.
In order to further improve the removal effect of the organic matters, as some possible embodiments of the present application, the amount of each component in the second layer of filler is further limited, that is, the weight parts of each component in the second layer of filler are as follows:
75-83 parts of modified activated carbon, 12-18 parts of modified chitosan and 8-11 parts of modified graphene oxide-carbon fiber.
In order to further improve the removal effect of the organic matters, as some possible embodiments of the present application, the amount of each component in the second layer of filler is further limited, that is, the weight parts of each component in the second layer of filler are as follows:
80 parts of modified activated carbon, 16 parts of modified chitosan and 10 parts of modified graphene oxide-carbon fiber.
In order to facilitate the taking and placing of the first layer of packing and the second layer of packing, as some embodiments of the application, the composite packing treatment unit comprises an adsorption tower and two placing barrels which are arranged in the adsorption tower in an up-and-down overlapping way; the placing barrel comprises a supporting filter plate and a coaming plate arranged around the supporting filter plate;
the two placing barrels are respectively connected with the inner wall of the adsorption tower in a sliding manner;
The top walls of the two placing barrels are provided with two handles, and the bottom wall of the placing barrel above is provided with a first slot for inserting the handle below; the adsorption tower roof is provided with the second slot that is used for inserting and establishes the top handle.
In addition, in order to achieve the purpose, the application also provides a treatment process of the high-difficulty and difficult-degradation salt-containing wastewater, which adopts the treatment equipment to treat the wastewater, and comprises the following steps:
s1, introducing high-difficulty nondegradable salt-containing wastewater to be treated into a coarse impurity filtering unit, and removing dregs in the wastewater to obtain wastewater subjected to primary treatment;
s2, introducing the wastewater subjected to the first treatment into a flocculation unit, sequentially adding a flocculant and a flocculation aid in the flocculation process, and obtaining wastewater subjected to the second treatment after flocculation treatment;
s3, introducing the wastewater subjected to the second treatment into a flocculate filtering unit to obtain wastewater subjected to the third treatment;
s4, introducing ozone into the wastewater subjected to the third treatment for catalytic oxidation treatment to obtain wastewater subjected to the fourth treatment;
s5, carrying out primary desalination and organic adsorption treatment on the fourth treated wastewater through a composite filler treatment unit to obtain fifth treated wastewater;
and S6, evaporating the wastewater from the fifth treatment to obtain wastewater from the sixth treatment.
The process for treating the high-difficulty and difficult-to-degrade salt-containing wastewater is further described in detail below with reference to the specific embodiments.
Example 1 (flow sheet as shown in FIG. 1)
S1, introducing high-difficulty degradation-resistant machine wastewater (COD is 3550mg/L, TDS is 6807mg/L, and pH is 7.3) to be treated into a coarse impurity filtering unit, wherein a coarse grating and a fine grating are arranged in the coarse impurity filtering unit so as to remove dregs in the wastewater, thereby obtaining wastewater treated for the first time;
s2, introducing the wastewater subjected to the first treatment into a flocculation unit, sequentially adding a flocculating agent (polyaluminium sulfate with the addition amount of 25 mg/L) and a flocculation aid (carboxymethyl chitosan grafted with acrylamide with the addition amount of 1 mg/L) in the flocculation process, and continuously stirring in the flocculation process to obtain wastewater subjected to the second treatment after flocculation treatment;
S3, introducing the second treated wastewater into a flocculation filtering unit, wherein the flocculation filtering unit comprises a filtering tank loaded with activated zeolite with 10-30 meshes, a multi-medium filter connected with the water outlet end of the filtering tank, and an ultrafiltration membrane connected with the water outlet end of the multi-medium filter, and treating the wastewater by the flocculation filtering unit to obtain third treated wastewater;
S4, introducing ozone into the wastewater subjected to the third treatment for catalytic oxidation treatment, wherein the addition amount of the ozone is 15mg/L, the treatment time is 30min, the catalyst is activated carbon loaded with copper-manganese oxide, the addition amount of the catalyst is 0.05mg/L, and after the treatment is finished, the wastewater subjected to the fourth treatment is obtained, and the COD (chemical oxygen demand) of the wastewater subjected to the fourth treatment is 900-950mg/L.
S5, introducing the wastewater subjected to the fourth treatment into a composite filler treatment unit, performing primary desalting and organic adsorption treatment through a first layer of filler (D3520 macroporous adsorption resin) on the upper layer, and performing deep adsorption of organic matters through a second layer of filler on the lower layer to obtain wastewater subjected to the fifth treatment, wherein the COD (chemical oxygen demand) of the wastewater subjected to the fifth treatment is 7.1mg/L.
Wherein the second layer of filler is formed by mixing 78 parts of modified activated carbon, 15 parts of modified chitosan and 10 parts of modified graphene oxide-carbon fiber; the first layer of filler is 1/3 of the total mass of the second layer of filler.
The two layers of fillers are cylindrical after being loaded, the diameter-to-height ratio of the second layer of fillers is 1:7, and the volume of wastewater passing through the composite filler treatment unit per hour is 3 times of the total volume of the first layer of fillers and the second layer of fillers.
And S5, carrying out desalination treatment on the wastewater treated in the fifth time through a triple-effect evaporation crystallizer to obtain wastewater treated in the sixth time.
The TDS of the wastewater treated for the sixth time (namely the final treated water) is less than or equal to 100mg/L.
Example 2
Compared with the embodiment 1, the dosage of each component in the second layer of filler is adjusted, and the adjusted second layer of filler has the following composition:
79 parts of modified activated carbon, 17 parts of modified chitosan and 8 parts of modified graphene oxide-carbon fiber.
The remaining steps and parameters were the same as in example 1.
Wherein the COD of the wastewater of the fifth time is 6.5mg/L; the TDS of the wastewater of the sixth time is less than or equal to 100mg/L.
Example 3
Compared with the embodiment 1, the dosage of each component in the second layer of filler is adjusted, and the adjusted second layer of filler has the following composition:
80 parts of modified activated carbon, 16 parts of modified chitosan and 10 parts of modified graphene oxide-carbon fiber.
The remaining steps and parameters were the same as in example 1.
Wherein the COD of the wastewater of the fifth time is 4.1mg/L; the TDS of the wastewater of the sixth time is less than or equal to 100mg/L.
Example 4
Because the actual regeneration time and regeneration method of the first layer of packing and the second layer of packing are not absolutely the same, the first layer of packing and the second layer of packing need to be separately arranged so as to be convenient for taking and placing the two layers of packing and regenerating each packing, and based on this, as shown in fig. 2, on the basis of embodiment 1, the composite packing treatment unit comprises an adsorption tower 1 and two placing barrels 2 which are arranged in the adsorption tower 1 in an overlapping way, wherein the two placing barrels 2 are cylindrical barrels and have the same inner diameter; the placement barrel 2 comprises a support filter plate 201 and a coaming 202 arranged around the support filter plate 201; a first layer of filling material is placed in the placing barrel 2 positioned above, and a second layer of filling material is placed in the placing barrel 2 positioned below; the support filter plate 201 is made of materials to meet micro-nano level filtering requirements, preferably nano filtering requirements. The two placing barrels 2 are respectively connected with the inner wall of the adsorption tower 1 in a sliding manner so as to facilitate taking and placing of the placing barrels 2. The internal diameter-to-height ratio of the lower placing barrel 2 is 1:5-1:8, and only the positions of the two placing barrels 2 are shown in fig. 2, and the internal diameter-to-height ratio of the lower placing barrel 2 is not strictly drawn; in this example, the inner diameter of the lower placement barrel 2 was 20cm and the inner height was 140cm, which is the same as the diameter of the second filler in example 1, and the lower placement barrel 2 was fully loaded with the second filler.
As shown in fig. 2, a top cover is detachably arranged at the top end of the adsorption tower 1, a liquid inlet pipe is arranged on the top cover, and a liquid outlet pipe is arranged at the bottom end of the adsorption tower 1; in practical implementation, a liquid separating disc (not shown in the drawings in the prior art) is arranged at the liquid outlet end of the liquid inlet pipe.
As shown in fig. 2 and 3, the top walls of the two placing barrels 2 are provided with two handles 3, and the bottom wall of the placing barrel 2 positioned above is provided with a first slot for inserting the lower handle 3; the top cover is provided with a second slot 4 for inserting the upper lifting handle 3.
Working principle: firstly, placing a placing barrel 2 loaded with a second layer of packing below the inside of an adsorption tower 1, then placing the placing barrel 2 loaded with a first layer of packing at the top end of the placing barrel 2 loaded with the second layer of packing, and when the placing barrel is placed, a handle 3 at the top end of the placing barrel 2 below is just inserted into a first slot at the bottom end of the placing barrel 2 above; and then the top cover is covered, the top cover can be limited by a limiting device such as a bolt, and in the process of covering the top cover, the handle 3 at the top end of the top placement barrel 2 is just positioned in the second slot 4 at the bottom end of the top cover. And then the wastewater is added into an adsorption tower through a liquid inlet pipe for adsorption treatment.
When any one or two layers of fillers are required to be regenerated or replaced, the top cover is opened, the lifting handle 3 at the upper part is lifted upwards, the placing barrel 2 at the upper part is taken down, the lifting handle 3 at the lower part is lifted upwards, the placing barrel 2 at the lower part is taken down, and the two layers of fillers can be regenerated.
Comparative example 1
Compared with example 1, the first filler layer was not provided, and the other steps and parameters were the same as in example 1.
COD of the wastewater of the fifth time is 79.1mg/L.
Therefore, the macroporous adsorption resin can primarily remove the salt in the wastewater so as to reduce the influence of the salt on the adsorption capacity of the composite filler, and if the macroporous adsorption resin is not added in the wastewater treatment process, the adsorption capacity of the composite filler on organic matters can be seriously influenced.
Comparative example 2
Compared with example 1, the second filler layer is completely replaced by modified activated carbon, and the rest steps and parameters are the same as those of example 1.
The COD of the wastewater of the fifth time is more than 70mg/L.
From this, it is understood that the adsorption capacity for organic matters is significantly reduced if modified chitosan and modified graphene oxide-carbon fibers are not added to the first filler.
Comparative example 3
Compared with example 1, the modified chitosan in the second filler layer was replaced with chitosan. The remaining steps and parameters were the same as in example 1.
The COD of the wastewater of the fifth time is more than 70mg/L.
In addition, the second filler of examples 1-3 and comparative examples 2-3 was monitored for long term operation as follows:
when the second-layer filler in the embodiment 1-3 is operated for 300h in an accumulated way, the COD of the organic matters is less than 150mg/L, then the three second-layer fillers are respectively regenerated, and after the regenerated second-layer filler adsorbs wastewater, the COD of the organic matters is less than 120mg/L, which indicates that the composite adsorbent in the embodiment 1-3 can still maintain higher adsorption efficiency when operated for a long time.
The COD of the organic matters in the second layer of filler in the comparative example 2 is more than 200mg/L when the second layer of filler is operated for 250 hours in an accumulated way, and then the second layer of filler is subjected to regeneration treatment, after the regenerated second layer of filler adsorbs wastewater, the COD of the organic matters is more than 200mg/L, which shows that the adsorption capacity of the second layer of filler in the comparative example 2 is lower than that of the second layer of filler in the examples 1-3 when the operation time is lower than that of the second layer of filler in the examples 1-3, and the adsorption efficiency after regeneration is also lower than that of the second layer of filler in the examples 1-3. The lack of abrasion-resistant lubricating substances (which causes the second filler layer to be severely extruded under the action of water pressure and to be more broken) and the lack of adsorbing substances to organic matters in comparative example 2 result in the reduction of the overall adsorption performance of the composite filler.
When the second-layer filler in the comparative example 3 is operated for 230 hours in an accumulated way, the COD of the organic matters is more than 200mg/L, then the second-layer filler is subjected to regeneration treatment, and after the regenerated second-layer filler adsorbs wastewater, the COD of the organic matters is more than 250mg/L, which shows that the chitosan in the comparative example 3 has a certain removal effect on the organic matters, but is fragile, and the structure of the chitosan is damaged in the long-time operation process, so that the overall adsorption performance of the second-layer filler is reduced; after regeneration, it is not resistant to high temperature, resulting in structural re-failure and further in serious degradation of the overall performance of the second filler layer.
Noteworthy are: in the long-time operation monitoring, the first layer of filler in the embodiment 1-3 and the comparative example 2-3 is required to keep stronger adsorption capacity all the time, and if the adsorption effect is obviously insufficient, the first layer of filler in the embodiment 1-3 and the comparative example 2-3 is required to be regenerated or replaced synchronously by a vertical horse.
To sum up: the composite filler in the embodiment 1-3 has a good organic matter adsorption effect in the initial operation and still has a good adsorption effect after 300 hours of accumulated operation, so that the service life of the composite filler is effectively prolonged.
Claims (10)
1. The high-difficulty degradation-resistant salt-containing wastewater treatment equipment is characterized by comprising a coarse impurity filtering unit, a flocculation unit, a flocculate filtering unit, an ozone catalytic oxidation unit, a composite filler treatment unit and an evaporation unit;
Wherein, a first layer of filler and a second layer of filler are distributed in the composite filler treatment unit up and down, and the first layer of filler is macroporous adsorption resin; the second layer of filler consists of modified activated carbon, modified chitosan and modified graphene oxide-carbon fiber; the first layer of filler and the second layer of filler form a composite filler;
wherein the modified activated carbon is copper-based activated carbon;
the modified chitosan is obtained by modifying chitosan by silicon dioxide and then grafting polyvinyl alcohol;
The modified graphene oxide-carbon fiber is obtained by grafting graphene oxide-carbon fiber with polyvinyl alcohol.
2. The high-difficulty degradation-resistant salt-containing wastewater treatment equipment according to claim 1, wherein the flocculating agent adopted by the flocculating unit is polyaluminium sulfate, and the flocculating aid is carboxymethyl chitosan grafted with acrylamide.
3. The high-difficulty degradation-resistant brine wastewater treatment facility according to claim 1, wherein the flocculate filtering unit comprises a filtering tank loaded with activated zeolite, a multi-media filter connected to the water outlet end of the filtering tank, and an ultrafiltration membrane connected to the water outlet end of the multi-media filter.
4. The high-difficulty degradation-resistant salt-containing wastewater treatment equipment according to claim 1, wherein in the ozone catalytic oxidation unit, activated carbon loaded with copper-manganese oxide is used as a catalyst.
5. The high-difficulty degradation-resistant salt-containing wastewater treatment device according to claim 1, wherein in the composite filler treatment unit, the mass ratio of the first layer of filler to the second layer of filler is 1:3-3.5.
6. The high-difficulty degradation-resistant salt-containing wastewater treatment equipment according to claim 5, wherein the second filler comprises the following components in parts by weight:
70-85 parts of modified activated carbon, 10-20 parts of modified chitosan and 5-13 parts of modified graphene oxide-carbon fiber.
7. The high-difficulty degradation-resistant salt-containing wastewater treatment equipment according to claim 5, wherein the second filler comprises the following components in parts by weight:
75-83 parts of modified activated carbon, 12-18 parts of modified chitosan and 8-11 parts of modified graphene oxide-carbon fiber.
8. The high-difficulty degradation-resistant salt-containing wastewater treatment equipment according to claim 5, wherein the second filler comprises the following components in parts by weight:
80 parts of modified activated carbon, 16 parts of modified chitosan and 10 parts of modified graphene oxide-carbon fiber.
9. The high-difficulty degradation-resistant salt-containing wastewater treatment equipment according to claim 1, wherein the composite filler treatment unit comprises an adsorption tower (1) and two placing barrels (2) which are arranged in the adsorption tower (1) in an up-down overlapping manner; the placing barrel (2) comprises a supporting filter plate (201) and a coaming plate (202) arranged around the supporting filter plate (201);
the two placing barrels (2) are respectively connected with the inner wall of the adsorption tower (1) in a sliding manner;
The top walls of the two placing barrels (2) are provided with two handles (3), and the bottom wall of the placing barrel (2) above is provided with a first slot for inserting the handle (3) below; the top wall of the adsorption tower (1) is provided with a second slot (4) for inserting the upper lifting handle (3).
10. A process for treating high-difficulty refractory salt-containing wastewater, which is characterized by adopting the treatment equipment as claimed in any one of claims 1-9 to treat, and comprising the following steps:
s1, introducing high-difficulty nondegradable salt-containing wastewater to be treated into a coarse impurity filtering unit, and removing dregs in the wastewater to obtain wastewater subjected to primary treatment;
s2, introducing the wastewater subjected to the first treatment into a flocculation unit, sequentially adding a flocculant and a flocculation aid in the flocculation process, and obtaining wastewater subjected to the second treatment after flocculation treatment;
s3, introducing the wastewater subjected to the second treatment into a flocculate filtering unit to obtain wastewater subjected to the third treatment;
s4, introducing ozone into the wastewater subjected to the third treatment for catalytic oxidation treatment to obtain wastewater subjected to the fourth treatment;
s5, carrying out primary desalination and organic adsorption treatment on the fourth treated wastewater through a composite filler treatment unit to obtain fifth treated wastewater;
and S6, evaporating the wastewater from the fifth treatment to obtain wastewater from the sixth treatment.
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