CN110759514A - High-concentration phosphorus-containing wastewater treatment method and treatment system for phenolic resin enterprises - Google Patents
High-concentration phosphorus-containing wastewater treatment method and treatment system for phenolic resin enterprises Download PDFInfo
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 54
- 239000011574 phosphorus Substances 0.000 title claims abstract description 54
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 30
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 30
- 238000004065 wastewater treatment Methods 0.000 title claims description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 87
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000002351 wastewater Substances 0.000 claims abstract description 41
- 239000002244 precipitate Substances 0.000 claims abstract description 36
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 23
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims abstract description 20
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims abstract description 17
- 239000004137 magnesium phosphate Substances 0.000 claims abstract description 17
- 229960002261 magnesium phosphate Drugs 0.000 claims abstract description 17
- 235000010994 magnesium phosphates Nutrition 0.000 claims abstract description 17
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 17
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 17
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 12
- MHJAJDCZWVHCPF-UHFFFAOYSA-L dimagnesium phosphate Chemical compound [Mg+2].OP([O-])([O-])=O MHJAJDCZWVHCPF-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910000395 dimagnesium phosphate Inorganic materials 0.000 claims abstract description 9
- 238000007599 discharging Methods 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims description 48
- 239000010802 sludge Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 9
- 239000010865 sewage Substances 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims 2
- 239000007787 solid Substances 0.000 claims 2
- 239000000149 chemical water pollutant Substances 0.000 abstract description 12
- 230000008014 freezing Effects 0.000 abstract description 5
- 238000007710 freezing Methods 0.000 abstract description 5
- 230000018044 dehydration Effects 0.000 description 14
- 238000006297 dehydration reaction Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 208000005156 Dehydration Diseases 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 9
- 239000001488 sodium phosphate Substances 0.000 description 9
- 229910000162 sodium phosphate Inorganic materials 0.000 description 9
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002686 phosphate fertilizer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052567 struvite Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- MXZRMHIULZDAKC-UHFFFAOYSA-L ammonium magnesium phosphate Chemical compound [NH4+].[Mg+2].[O-]P([O-])([O-])=O MXZRMHIULZDAKC-UHFFFAOYSA-L 0.000 description 1
- CKMXBZGNNVIXHC-UHFFFAOYSA-L ammonium magnesium phosphate hexahydrate Chemical compound [NH4+].O.O.O.O.O.O.[Mg+2].[O-]P([O-])([O-])=O CKMXBZGNNVIXHC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/121—Treatment of sludge; Devices therefor by de-watering, drying or thickening by mechanical de-watering
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The invention discloses a method for treating high-concentration phosphorus-containing wastewater of phenolic resin enterprises, which comprises the steps of adopting a step-by-step precipitation method, adding magnesium oxide in the first step to adjust the pH value to 6-7, adding magnesium sulfate, converting phosphorus into magnesium hydrogen phosphate precipitate, and immediately discharging the precipitate out of a system; adding magnesium oxide to adjust the pH value to 8-10.5, adding magnesium sulfate, and converting phosphorus into magnesium phosphate precipitate; the solid-liquid separation of the precipitate obtained in the two steps is carried out by a vacuum dehydrator immediately. The treatment method of the invention, the magnesium phosphate salt obtained by step-by-step treatment can be used for treating the aged landfill leachate; according to the method, the precipitate generated in the reactor is immediately treated by the vacuum dehydrator, so that the technical problem of kettle freezing is avoided, the treatment system is simplified, and the management is convenient.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to high-concentration phosphorus-containing wastewater treatment in phenolic resin enterprises.
Background
High-concentration phosphorus-containing organic wastewater can be generated in the production process of the phenolic resin, the content of sodium phosphate can reach 30-35%, and the COD is about 6 ten thousand mg/L. The biological method for treating the high-salinity organic wastewater has requirements on the salinity, and the biological method is not practical after dilution for the high salinity. The direct incineration mode is adopted for treatment, the heat value of the wastewater needs to be evaluated, and a unit with corresponding qualification needs to be entrusted for treatment. The evaporation concentration-cooling crystallization process is not suitable for high-salinity wastewater with COD as high as 6 ten thousand mg/L, although the evaporation-thermal crystallization process is suitable for treating the high-COD and high-salinity wastewater, has no special requirements on the types of soluble salts, has higher salt content and higher separation efficiency, and has a difficult problem in the deep treatment and recycling of salt mud or salt slag generated by thermal crystallization. If the evaporation-thermal crystallization process is adopted for treatment, not only the investment cost and the operation cost are both high (the evaporation cost is about 200-3) And the resulting salt sludge may still be disposed of as hazardous waste. In addition to the above methods, there is a chemical precipitation method in which phosphorus is removed by converting phosphate into insoluble phosphate precipitate by reaction with iron, aluminum or calcium salt, which produces a large amount of chemical sludge, and the sludge needs to be treated secondarily by incineration or the like and is difficult to be recycled.
The old landfill leachate has the outstanding characteristic of high ammonia nitrogen concentration reaching thousands of mg/L. The C/N is too low due to the excessively high ammonia nitrogen concentration, a carbon source required by biological denitrification is seriously insufficient, a certain inhibiting effect is realized on the conventional biological treatment, and the difficulty of biochemical treatment of the percolate is increased. The method is also the main reason that the total nitrogen removal rate is not high in the process of treating the percolate of most domestic refuse landfill sites. By magnesium ammonium phosphate process (Mg)2++PO4 3-+NH4++6H2O→MgNH4PO4·6H2O↓，MgNH4PO4·6H2MAP for short) for the pretreatment of old landfill leachateHigh efficiency, simple process and the formed precipitate can be recovered as slow release fertilizer, but the precipitant has large dosage and high cost.
A traditional treatment system for phosphorus-containing wastewater generally comprises a sedimentation tank and a flocculation tank which are combined, wherein a medicament is added into the sedimentation tank for sedimentation treatment, the treated wastewater is discharged into the flocculation tank, a flocculating agent is added into the flocculation tank for strengthening sedimentation, the wastewater is discharged into a secondary sedimentation tank for realizing solid-liquid separation, and then a filter press is used for dewatering. The system for treating sewage by combining the multi-stage tanks has large occupied space of the device, complex system and increased cost; the treatment method adopts a precipitation mode to separate the salt mud, so that the precipitation effect is poor, and time and labor are wasted.
Disclosure of Invention
The invention provides a method and a system for treating high-concentration phosphorus-containing wastewater in phenolic resin enterprises, which can solve the problems in the prior art,
the technical scheme of the invention is as follows:
a method for treating high-concentration phosphorus-containing wastewater of phenolic resin enterprises comprises the following steps:
1) conveying the high-concentration phosphorus-containing wastewater to a precipitation reactor, and adding magnesium oxide into the precipitation reactor to adjust the pH value to 6-7;
2) adding magnesium sulfate into the precipitation reactor in the step (1), and fixing most of phosphorus in the wastewater in magnesium hydrogen phosphate precipitation; stirring, immediately discharging the generated precipitate to a vacuum dehydrator for solid-liquid separation, refluxing the obtained filtrate to the precipitation reactor, and collecting the dehydrated sludge;
3) when the precipitation reactor in the step (2) does not produce any precipitate any more, adding magnesium oxide into the precipitation reactor to adjust the pH value to 8-10.5;
4) adding magnesium sulfate into the precipitation reactor in the step (3) to convert phosphorus in the reaction liquid into magnesium phosphate, continuously stirring, immediately discharging the generated magnesium phosphate precipitate to a vacuum dehydrator for solid-liquid separation, refluxing the obtained filtrate to the precipitation reactor, and collecting the dehydrated sludge;
5) and (4) when the precipitation reactor does not produce precipitates any more, conveying the residual filtrate in the precipitation reactor to a sewage biochemical treatment system.
The method comprises the steps of adding magnesium oxide into a precipitation reactor, reasonably controlling the pH value in the precipitation reactor, adding magnesium sulfate to convert sodium phosphate into magnesium hydrogen phosphate and magnesium phosphate precipitate, immediately discharging the generated precipitate to a vacuum dehydrator for dehydration treatment, reacting while dehydrating, and immediately performing solid-liquid separation, thereby avoiding the problem of kettle freezing. The sediment is treated by the vacuum dehydrator, so that the technical problems that the traditional filter press needs frequent plate disassembly and mud disassembly and pipeline blockage are solved.
Preferably, at least two vacuum dewaterers for performing solid-liquid separation are arranged, and each vacuum dewaterer comprises a first vacuum dewaterer and a second vacuum dewaterer which are respectively connected with the precipitation reactor; and after the precipitate is treated by the first vacuum dehydrator and the second vacuum dehydrator, the filtrate flows back to the precipitation reactor. In the reaction process, because the speed of generating the precipitate is high, the processing speed of one vacuum dehydrator is low, engineering accidents are easy to occur, and the engineering safety is ensured by adopting at least two vacuum dehydrators.
Preferably, the precipitates generated in the step (2) and the step (4) are conveyed to the first vacuum dehydrator and/or the second vacuum dehydrator for solid-liquid separation, the obtained filtrate flows back to the precipitation reactor, and the dehydrated sludge is collected.
Preferably, the residual filtrate in the precipitation reactor in the step (5) is conveyed to a filtrate tank, and the filtrate is conveyed to a sewage biochemical treatment system as a nutrient solution by the filtrate tank.
A high-concentration phosphorus-containing wastewater treatment system for phenolic resin enterprises comprises a precipitation reactor and a vacuum dehydrator, wherein the vacuum dehydrator is connected with the precipitation reactor through a delivery pump, and the precipitation reactor is connected with a subsequent biochemical treatment system; the vacuum dewatering device is used for carrying out solid-liquid separation on the precipitate generated by the precipitation reactor, and a filtrate reflux device is arranged between the vacuum dewatering device and the precipitation reactor and is used for refluxing the filtrate obtained by the vacuum dewatering device to the precipitation reactor; the sludge collecting device is used for collecting sludge generated by the vacuum dehydrator; and a filtrate conveying device is arranged between the precipitation reactor and the subsequent biochemical treatment system and is used for discharging the residual filtrate in the precipitation reactor to the subsequent biochemical treatment system.
Preferably, a stirring device and/or a pH detection device are/is arranged in the precipitation reactor.
Preferably, the number of the vacuum dewaterers is at least two, and the vacuum dewaterers are respectively connected with the precipitation reactor through a conveying pump.
Preferably, the precipitation reactor is further connected with a filtrate tank, the residual filtrate in the precipitation reactor is conveyed to the filtrate tank through an evacuation pump, and the filtrate in the filtrate tank is conveyed to a sewage biochemical treatment system through a filtrate lifting pump.
Preferably, the precipitation reactor is provided with a medicament adding device for adding magnesium oxide for adjusting the pH value and magnesium sulfate as a precipitator.
Preferably, the remaining filtrate in the precipitation reactor, the filtrate in the filtrate tank, is transported by a pump.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the invention relates to a method for treating high-concentration phosphorus-containing wastewater of a phenolic resin enterprise, which is based on the analysis of the water quality characteristics of aged landfill leachate and the denitrification technology, and takes the high-phosphorus wastewater in the production process of the phenolic resin enterprise as a raw material for producing magnesium phosphate salts; the magnesium phosphate obtained by the treatment method can be used for treating aged landfill leachate, and an efficient and low-cost nitrogen removal agent is found for the pretreatment of the aged landfill leachate; compared with the traditional treatment method, the treatment method avoids adding the flocculating and precipitating agent after the precipitation reaction to strengthen the precipitation effect, thereby avoiding the technical problems that a flocculation tank and a sedimentation tank are required to be combined and the treatment process is complicated; the treatment method adopts the vacuum dehydrator for precipitation treatment, and the solid-liquid separation is carried out while the reaction is carried out, so that the process flow is simplified, and the system operation management is convenient.
Secondly, according to the method for treating the high-concentration phosphorus-containing wastewater of the phenolic resin enterprise, the precipitate is quickly generated in the dosing reaction process, and the generated precipitate is immediately discharged to a vacuum dehydrator for treatment, so that the technical problem of kettle freezing is solved; adopt the vacuum dehydration machine to carry out solid-liquid separation, mud is carried while dehydrating, when having avoided traditional pressure filter to handle, and the rear end can't be carried to the tight mud cake layer, needs often to tear the board and unloads mud, and the pipeline also can be blockked up technical problem.
Thirdly, the method for treating the high-concentration phosphorus-containing wastewater of the phenolic resin enterprises does not cause secondary pollution, and the residual filtrate finally generated in the precipitation reactor can be used as a phosphate fertilizer of a wastewater biochemical treatment system of the phenolic resin enterprises, so that the dosage of the original phosphorus-containing nutrient solution of the wastewater biochemical system is reduced or the original phosphorus-containing nutrient solution is not required to be added, and the cost is reduced; the salt mud or salt slag obtained by treatment is magnesium hydrogen phosphate and magnesium phosphate precipitate, can be used as a high-efficiency nitrogen removal agent for high-ammonia-nitrogen wastewater such as aged landfill leachate, and achieves the environment-economic win-win effect of resource utilization of waste.
Fourthly, according to the method for treating the high-concentration phosphorus-containing wastewater of the phenolic resin enterprise, the salt and mud are separated by adopting a vacuum dehydration mode instead of a precipitation mode, so that the treatment effect is prevented from being influenced due to poor precipitation effect, precipitation and dehydration are combined into one, and the process flow is simplified.
Fifthly, the high-concentration phosphorus-containing wastewater treatment system of the phenolic resin enterprise adopts the vacuum dehydrator for solid-liquid separation, so that the situation that a sedimentation tank and a flocculation tank are required to be combined in the traditional wastewater treatment system is eliminated, the system is simplified, and the operation management of the system is facilitated; the technical problems that the traditional filter press needs frequent plate disassembly and mud disassembly and pipeline blockage are solved; the treatment system of the invention has simple equipment, low investment and low energy consumption for operation.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention;
fig. 2 is a schematic system flow diagram according to embodiment 1 of the present invention.
Detailed Description
The treatment object of the invention is high-phosphorus waste liquid in the production process of phenolic resin enterprises, phosphorus in the waste liquid exists in the form of sodium phosphate, the content of the sodium phosphate is up to 30-35%, even the content of the sodium phosphate in the concentrated waste liquid is doubled to reach 60-70%, and the corresponding total phosphorus concentration is close to 20 ten thousand mg/L. The existence form of sodium phosphate in wastewater is influenced by pH, the existence form of sodium phosphate is different, and the obtained precipitate is also different, so the control of the pH in the reaction process is particularly critical in order to obtain a specific precipitate, and the expected product cannot be obtained if the pH is improperly controlled.
The method adopts a step-by-step precipitation method, wherein the pH value of the wastewater is adjusted to 6-7 in the first step, and the dihydric phosphate in the wastewater is converted into the hydrogenphosphate, so that the hydrogenphosphate reacts with the magnesium sulfate added subsequently to generate magnesium hydrogenphosphate precipitate, and solid-liquid separation is carried out; and secondly, adjusting the pH value to 8-10.5, adding magnesium sulfate to generate magnesium phosphate precipitate, and performing solid-liquid separation, wherein phosphorus in the wastewater mainly exists in the forms of hydrogen phosphate and phosphate. Through fractional precipitation, the phosphorus in the waste liquid is finally reduced to the range that can be accepted by a subsequent biochemical treatment system as a phosphate fertilizer.
Based on the analysis of the water quality characteristics and denitrification technology of the aged landfill leachate, the high-phosphorus wastewater in the production process of phenolic resin enterprises is used as a raw material for producing magnesium phosphate for resource utilization, and the magnesium phosphate can be further used as an efficient nitrogen removal agent in the treatment process of high-ammonia nitrogen wastewater such as landfill leachate and the like. Thus, the method is feasible for phenolic resin manufacturers in terms of both technology and marketing of magnesium phosphate.
The invention simultaneously adopts magnesium sulfate as a precipitator, and does not select other precipitants such as calcium salt, because the phosphorus in the phosphorus-containing wastewater of the invention exists in the form of sodium phosphate, and the invention takes the high-phosphorus wastewater as a raw material for producing magnesium phosphate salt. Because of this form of phosphorus and the particular nature of the treatment objective, the present invention employs magnesium sulfate as a precipitating agent.
In the wastewater treatment process of the invention, solid-liquid separation is also important. Because the concentration of sodium phosphate in the wastewater is very high, precipitation is rapidly generated in the dosing reaction process, and the problem of kettle freezing can occur if solid-liquid separation is not performed in time. In addition, the generated precipitate has good dehydration performance, and reasonable dehydration equipment needs to be selected. The wastewater treatment method of the invention designs a way of reaction and dehydration, which is different from the traditional way of precipitation and dehydration after reaction, and adopts a vacuum dehydrator instead of a filter press.
The common dehydration equipment is a plate-frame or membrane filter press, and is suitable for materials with poor dehydration property, such as biological sludge. The vacuum dehydrator is adopted, so that the problem cannot be caused, the materials on the vacuum dehydrator are dehydrated on the transmission belt, filtrate can be sucked into the separation tank under the vacuum effect, the materials are conveyed while being dehydrated along with the rolling of the rotating belt, and the water content of the finally dehydrated materials is about 40-60%.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In practice, the invention will be understood to cover all modifications and variations of this invention provided they come within the scope of the appended claims.
Example 1
The embodiment provides a high concentration phosphorus wastewater treatment system of phenolic resin enterprise, including precipitation reactor 1, filtrating jar 2, vacuum dehydration machine 3, conveyer 5 and adsorption reactor 6. The precipitation reactor 1 is connected with a vacuum dehydrator 3 through a delivery pump, the precipitation reactor 1 is a high-concentration phosphorus-containing wastewater processor, the adsorption reactor 2 is an old garbage leachate processor, and the precipitation reactor 1 is provided with a dosing device, a pH detection device and a stirring device.
In order to ensure that the generated precipitate can be processed in time, the precipitation reactor is also connected with a second vacuum dehydrator so as to ensure the engineering safety and improve the processing efficiency of the precipitate.
The embodiment provides a method for treating high-concentration phosphorus-containing wastewater of phenolic resin enterprises, the high-concentration phosphorus-containing wastewater is pumped into a precipitation reactor, magnesium oxide is added to adjust the pH value to 6-7, magnesium sulfate is continuously added, most of phosphorus in the wastewater is fixed in magnesium hydrogen phosphate precipitation, the precipitation reactor is continuously stirred, meanwhile, a valve of a delivery pump is opened, the generated precipitation is delivered to a vacuum dehydrator through the delivery pump, filtrate flows back to the precipitation reactor, and filter-pressed sludge enters a conveyor.
And after the magnesium sulfate is added, closing the valve of the delivery pump. And continuously adding magnesium oxide into the precipitation reactor to adjust the pH value to 8-10.5, and continuously adding magnesium phosphate to convert phosphorus in the reaction liquid into magnesium phosphate so as to reduce the phosphorus concentration in the final residual liquid, so that the phosphorus can be accepted by a subsequent biochemical treatment system as a phosphate fertilizer. The precipitation reactor continuously stirs, simultaneously opens the delivery pump valve, and the sediment is carried to second vacuum dehydration machine 4 through the delivery pump, and the filtrating backward flow is to precipitation reactor, and filter-pressing mud gets into the conveyer.
And conveying the residual filtrate in the precipitation reactor to a filtrate tank through an emptying pump, and conveying the filtrate serving as nutrient solution to a sewage biochemical treatment system by using a filtrate lifting pump. And transporting the materialized sludge collected by the conveyor to a landfill for removing ammonia nitrogen in the aged landfill leachate. And respectively adding the aged landfill leachate and magnesium phosphate of the materialized sludge into an adsorption reactor, after the reaction is finished, feeding the residual waste liquid into a subsequent landfill leachate biochemical treatment system, and using a deposition product which is struvite as a fertilizer.
In the embodiment, magnesium oxide is added in batches, the pH value in a precipitation reactor is controlled to be 6-7 for the first time, and magnesium sulfate is added and stirred to obtain magnesium hydrogen phosphate precipitate; and controlling the pH value to be 8-10.5 for the second time, adding magnesium sulfate, and stirring to obtain magnesium phosphate precipitate. And after the precipitate is generated, the precipitate is timely discharged to a vacuum dehydrator for dehydration treatment, and solid-liquid separation and dehydration treatment are carried out while reaction is carried out, so that the problem of kettle freezing is avoided. Simultaneously, the vacuum dewatering machine is used for dewatering, sludge on the vacuum dewatering machine is dewatered on the transmission belt, filtrate is sucked into the separation tank under the vacuum effect, the sludge is conveyed while being dewatered along with the transmission of the transmission belt, and the water content of the finally dewatered sludge is about 40-60%. The problem that the conventional filter press needs to frequently disassemble plates to disassemble mud is solved, and the technical problem of pipeline blockage is solved.
The main components of the sludge collected by the embodiment are magnesium hydrogen phosphate and magnesium phosphate, and the sludge can be used as a high-efficiency nitrogen removing agent for high ammonia nitrogen wastewater such as aged landfill leachate, so that the environment-economic win-win effect of resource utilization of waste is achieved.
In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
Claims (10)
1. A method for treating high-concentration phosphorus-containing wastewater of phenolic resin enterprises is characterized by comprising the following steps:
1) conveying the high-concentration phosphorus-containing wastewater to a precipitation reactor, and adding magnesium oxide into the precipitation reactor to adjust the pH value to 6-7;
2) adding magnesium sulfate into the precipitation reactor in the step (1), and fixing most of phosphorus in the wastewater in magnesium hydrogen phosphate precipitation; stirring, immediately discharging the generated precipitate to a vacuum dehydrator for solid-liquid separation, refluxing the obtained filtrate to the precipitation reactor, and collecting the dehydrated sludge;
3) when the precipitation reactor in the step (2) does not produce any precipitate any more, adding magnesium oxide into the precipitation reactor to adjust the pH value to 8-10.5;
4) adding magnesium sulfate into the precipitation reactor in the step (3) to convert phosphorus in the reaction liquid into magnesium phosphate, continuously stirring, immediately discharging the generated magnesium phosphate precipitate to a vacuum dehydrator for solid-liquid separation, refluxing the obtained filtrate to the precipitation reactor, and collecting the dehydrated sludge;
5) and (4) when the precipitation reactor does not produce precipitates any more, conveying the residual filtrate in the precipitation reactor to a sewage biochemical treatment system.
2. The method for treating high-concentration phosphorus-containing wastewater of phenolic resin enterprises as claimed in claim 1, wherein at least two vacuum dewatering machines for performing the solid-liquid separation are provided, and the vacuum dewatering machines comprise a first vacuum dewatering machine and a second vacuum dewatering machine, which are respectively connected to the precipitation reactor.
3. The method for treating high-concentration phosphorus-containing wastewater of phenolic resin enterprises of claim 2, wherein the precipitates generated in the steps (2) and (4) are subjected to solid-liquid separation by the first vacuum dehydrator and/or the second vacuum dehydrator, the obtained filtrate is refluxed to the precipitation reactor, and the dehydrated sludge is collected.
4. The method for treating the high-concentration phosphorus-containing wastewater of the phenolic resin enterprise as recited in claim 1, wherein the residual filtrate in the precipitation reactor in the step (5) is conveyed to a filtrate tank, and the filtrate is conveyed to a sewage biochemical treatment system by the filtrate tank.
5. The high-concentration phosphorus-containing wastewater treatment system of the phenolic resin enterprise is characterized by comprising a precipitation reactor and a vacuum dehydrator, wherein the vacuum dehydrator is connected with the precipitation reactor through a delivery pump, and the precipitation reactor is also connected with a subsequent biochemical treatment system; the vacuum dewatering device is used for filtering the solid and liquid in the precipitation reactor, and is used for filtering the solid and liquid in the precipitation reactor; the sludge collecting device is used for collecting sludge generated by the vacuum dehydrator; and a filtrate conveying device is arranged between the precipitation reactor and the subsequent biochemical treatment system and is used for discharging the residual filtrate in the precipitation reactor to the subsequent biochemical treatment system.
6. The phenolic resin enterprise high-concentration phosphorus-containing wastewater treatment system as claimed in claim 1, wherein a stirring device and/or a pH detection device is/are arranged in the precipitation reactor.
7. The high-concentration phosphorus-containing wastewater treatment system of the phenolic resin enterprise as claimed in claim 1, wherein the number of the vacuum dewaterers is at least two, and the vacuum dewaterers are respectively connected with the precipitation reactor through a conveying pump.
8. The high-concentration phosphorus-containing wastewater treatment system of the phenolic resin enterprise as claimed in claim 1, wherein the precipitation reactor is further connected with a filtrate tank, the residual filtrate in the precipitation reactor is conveyed to the filtrate tank, and the filtrate in the filtrate tank is conveyed to a sewage biochemical treatment system.
9. The phenolic resin enterprise high-concentration phosphorus-containing wastewater treatment system as claimed in claim 1, wherein the precipitation reactor is provided with a medicament adding device for adding magnesium oxide for adjusting the pH value and magnesium sulfate as a precipitator.
10. The phenolic resin enterprise high-concentration phosphorus-containing wastewater treatment system as claimed in claim 8, wherein the residual filtrate in the precipitation reactor and the filtrate in the filtrate tank are conveyed by a pump.
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