CN110372143A - Landfill leachate physicochemical deamination pretreatment method and device - Google Patents
Landfill leachate physicochemical deamination pretreatment method and device Download PDFInfo
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- CN110372143A CN110372143A CN201910656166.1A CN201910656166A CN110372143A CN 110372143 A CN110372143 A CN 110372143A CN 201910656166 A CN201910656166 A CN 201910656166A CN 110372143 A CN110372143 A CN 110372143A
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- 239000000149 chemical water pollutant Substances 0.000 title claims abstract description 68
- 230000009615 deamination Effects 0.000 title claims abstract description 27
- 238000006481 deamination reaction Methods 0.000 title claims abstract description 27
- 238000002203 pretreatment Methods 0.000 title claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 208
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 104
- 238000001704 evaporation Methods 0.000 claims abstract description 80
- 230000008020 evaporation Effects 0.000 claims abstract description 80
- 238000010521 absorption reaction Methods 0.000 claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000006228 supernatant Substances 0.000 claims abstract description 26
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 29
- 239000002351 wastewater Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 17
- 238000004062 sedimentation Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 239000012452 mother liquor Substances 0.000 claims description 5
- 150000007524 organic acids Chemical class 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 17
- 239000003513 alkali Substances 0.000 abstract description 10
- 150000003863 ammonium salts Chemical class 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 239000007787 solid Substances 0.000 abstract description 5
- 238000007781 pre-processing Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000005086 pumping Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000005587 carbonate group Chemical group 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- -1 ammonium ions Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/12—Separation of ammonia from gases and vapours
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/06—Contaminated groundwater or leachate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Water Treatments (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
Abstract
The invention provides a method and a device for preprocessing landfill leachate by physicochemical deamination, which comprises the following steps: (1) conveying the landfill leachate to a pretreatment unit to realize solid-liquid separation, and adding a carbonate decomposition auxiliary agent into the supernatant; (2) and (3) conveying the supernatant of the pretreatment unit to a negative pressure evaporation unit, carrying out negative pressure evaporation until the pH of the supernatant is greater than 9, and conveying the liquid subjected to negative pressure evaporation to an ammonia stripping unit. According to the method, the carbonate decomposition auxiliary agent is added into the landfill leachate, and negative pressure evaporation is matched to ensure that the ammonia nitrogen in the landfill leachate can be effectively removed without consuming alkali to adjust the pH value of the landfill leachate; according to the invention, the absorption process and the equipment structure are optimized, the gas-liquid ratio is controlled to be 500-plus 2000:1 during ammonia stripping, the energy consumption is reduced, and meanwhile, the rich solution is directly cooled, crystallized and separated to obtain the solid ammonium salt, so that the energy consumption is greatly reduced.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to a method and equipment for preprocessing landfill leachate by physicochemical deamination.
Background
With the rapid development of the economy and the urbanization construction of China, the living standard of people is continuously improved, and a large amount of urban domestic garbage is generated. The sanitary landfill is the main disposal measure of domestic garbage in China, in recent years, along with increasingly strict environmental requirements, the proportion of garbage incineration power generation is on the trend of increasing year by year, but both the two disposal measures can generate a large amount of garbage percolate in the disposal process. The landfill leachate is high-concentration organic wastewater which is complex in property and difficult to treat, has the characteristics of high COD (chemical oxygen demand), high ammonia nitrogen, high salt, toxicity and the like, if the landfill leachate is not treated, the toxic and harmful pollutants can cause serious harm to the surrounding environment of a receiving water body, animals, plants and human beings, and the social influence is huge.
The landfill leachate has high B/C and good biodegradability, but high ammonia nitrogen causes C/N imbalance and cannot meet the requirements of microbial nutrition conditions of 100:5: 1C: N: P, so that a large biochemical pool, long retention time and carbon source supplement are required for biochemical treatment, and the ammonia nitrogen in tail water is difficult to discharge stably and up to the standard. In order to ensure the stable standard discharge of tail water in actual engineering, advanced treatment such as chemical oxidation, membrane filtration, reverse osmosis and the like needs to be carried out on the tail water, so that the integral treatment process of the landfill leachate is complex, the flow is long, the engineering investment is large, the occupied area is large, and the operation cost is high. Therefore, the deamination pretreatment of the landfill leachate is enhanced, which is beneficial to simplifying the process flow, shortening the retention time of biochemical treatment of wastewater, reducing the investment and operation cost and simplifying the operation and management; meanwhile, a large amount of ammonia nitrogen contained in the leachate also has great recycling value.
At present, common deaminizing treatment technologies for landfill leachate in industry mainly include air stripping, breakpoint chlorination, chemical precipitation (MAP), adsorption, advanced oxidation (ozone oxidation, Fenton oxidation, electrochemical oxidation, photocatalytic oxidation, persulfate oxidation, ultrasonic oxidation, etc.), membrane absorption, and the like. Wherein, the air stripping method has simple process, easy operation, maturity and effectiveness, and wide industrial application.
The stripping method has good ammonia nitrogen removal efficiency only under a high pH value, and the pH value is usually controlled to be about 10, so that a large amount of alkali is consumed, the consumption of a medicament is large, and the operation cost is high; the pH of the blow-off effluent needs to be adjusted back, a large amount of materialized sludge hazardous waste (when the pH is adjusted by lime, calcium hydroxide and the like) or high-salinity wastewater (when the pH is adjusted by sodium hydroxide and the like) is generated, and the operation cost is increased by the treatment of the materialized sludge hazardous waste; the high salt-containing wastewater increases the difficulty of subsequent biochemical treatment, even needs desalination treatment, and further increases the operation cost. Therefore, the research and development of a novel process for removing ammonia nitrogen from landfill leachate can obviously reduce the running cost of removing ammonia nitrogen while efficiently removing ammonia nitrogen, simplify the subsequent biochemical treatment process, investment and running cost, and can carry out low-cost recovery and recycling on ammonia nitrogen in the leachate, thereby being a key technology which is urgently required for treating leachate in numerous landfill sites and incineration plants at present.
At present, ammonia nitrogen in landfill leachate is removed by adopting a stripping method in some patents of landfill leachate treatment. In patent CN102329057B, the landfill leachate is neutralized and precipitated by lime and then sent to an ammonia stripping tower for deamination treatment; in the invention patent CN108395048A, after the landfill leachate is subjected to coagulating sedimentation, the pH of the supernatant is adjusted to 10.0-11.0 by NaOH, and then the supernatant enters an ammonia stripping tower for ammonia stripping, the ammonia nitrogen removal of the landfill leachate in the two patents mainly adopts a stripping method to remove ammonia nitrogen, the equipment mainly comprises a stripping tower and an aeration tank, before the landfill leachate enters stripping equipment, alkali such as lime, calcium hydroxide or sodium hydroxide is adopted to adjust the pH value, but the improvement of stripping efficiency and operation cost is not involved.
Because ammonia nitrogen in the landfill leachate mainly exists in the form of ammonium ions of carbonate or weak organic acid salt, when the ammonia nitrogen in the landfill leachate is removed by adopting a stripping method, the pH value of the landfill leachate is regulated by adding alkali, so that the ammonium ions are converted into free ammonia and can be removed by stripping, and the consumption of the alkali is high; meanwhile, the ammonia stripping method belongs to gas film mass transfer control, and needs larger gas flow and gas-liquid interface, and the gas-liquid ratio of the traditional packed tower ammonia stripping tower is usually controlled at 3000-plus 5000:1, so that the power consumption is large. Therefore, the key to the ammonia stripping method is how to reduce the alkali consumption and the gas-liquid ratio on the premise of ensuring better ammonia stripping efficiency.
Disclosure of Invention
The invention provides a method and equipment for performing physicochemical deamination pretreatment on landfill leachate, which are used for solving the problems that ammonia nitrogen stripping can be performed only by adjusting the pH value of the landfill leachate with soda lime in the prior art and the energy consumption in the ammonia nitrogen recovery process is high.
In a first aspect, the invention provides a landfill leachate materialization deamination pretreatment method, which comprises the following steps:
(1) conveying the landfill leachate to a pretreatment unit to realize solid-liquid separation, and adding a carbonate decomposition auxiliary agent into the supernatant;
(2) and (3) conveying the supernatant of the pretreatment unit to a negative pressure evaporation unit, carrying out negative pressure evaporation until the pH of the supernatant is greater than 9, and conveying the liquid subjected to negative pressure evaporation to an ammonia stripping unit.
Further, still include:
(3) and conveying the gas subjected to ammonia stripping and the gas subjected to negative pressure evaporation to an ammonia recovery unit.
Further, the negative pressure evaporation unit in the step (2) comprises a negative pressure evaporation tower, the operating pressure of the negative pressure evaporation tower is-0.1 MPa to-0.06 MPa, preferably-0.08 MPa to-0.06 MPa when negative pressure evaporation is carried out, and the heating temperature is 60 ℃ to 100 ℃, preferably 60 ℃ to 80 ℃.
The carbonate decomposition auxiliary agent in the step (1) can promote the decomposition of carbonate in the supernatant of the landfill leachate, particularly under the condition of negative pressure evaporation, the pH value of the supernatant can be increased to 9-11, and alkali or lime is not needed to enter a subsequent ammonia stripping unit.
Further, in the step (2), before the supernatant liquid of the pretreatment unit is conveyed to the negative pressure evaporation unit, the temperature of the supernatant liquid is increased to 60 ℃.
Further, the pH value of the liquid part after negative pressure evaporation in the step (3) is 9-11, and the ammonia nitrogen concentration is less than 500 mg/L.
Further, the ammonia stripping unit in the step (3) comprises a stripping tower, wherein the gas-liquid ratio in the stripping tower is 500-2000:1, the stripping temperature is 30-60 ℃, and the generated tail gas is conveyed to the ammonia recovery unit.
Further, the ammonia recovery unit in the step (3) comprises an ammonia absorption tower, the ammonia absorption solution is an aqueous solution of an organic acid and/or an inorganic acid, the inorganic acid is preferably sulfuric acid, hydrochloric acid, phosphoric acid and carbonic acid, and the organic acid is preferably citric acid; the ammonia absorbing solution has a pH of less than 3.
Further, the absorption temperature in the ammonia absorption tower is 40-50 ℃.
Further, the ammonia recovery unit further comprises a cooling crystallizer, and when the rich liquid after ammonia absorption in the ammonia absorption tower is close to saturation, the rich liquid is conveyed to the cooling crystallizer.
Further, the cooled and precipitated crystals are filtered and refined by the cooling crystallizer under the condition that the cooling temperature is 20-30 ℃, and mother liquor is conveyed to the ammonia absorption tower; the cooling temperature is preferably 22 ℃.
Further, the negative pressure evaporation tower and the stripping tower are respectively any one of a packed tower or a plate tower; the packed tower adopts a bulk pile with anti-blocking performance, and the packing takes pall rings as base materials and is subjected to anti-blocking modification on the surface; the plate tower adopts an anti-blocking tower plate.
In a second aspect, the invention provides a landfill leachate materialization deamination pretreatment device, which comprises: the device comprises a pretreatment unit, a negative pressure evaporation unit, an ammonia stripping unit and an ammonia recovery unit; wherein,
the pretreatment unit comprises a wastewater adjusting sedimentation tank and a carbonate decomposition auxiliary agent storage tank which are connected, the negative pressure evaporation unit comprises a negative pressure evaporation tower, the ammonia stripping unit comprises a stripping tower, and the ammonia recovery unit comprises an ammonia absorption tower and a cooling crystallizer; wherein,
the pretreatment unit comprises a wastewater adjusting sedimentation tank and a carbonate decomposition auxiliary agent storage tank which are connected, the negative pressure evaporation unit comprises a negative pressure evaporation tower, the ammonia stripping unit comprises a stripping tower, and the ammonia recovery unit comprises an ammonia absorption tower; wherein,
the water inlet at the upper part of the negative pressure evaporation tower is connected with the water outlet of the wastewater adjusting sedimentation tank;
the water inlet at the upper part of the stripping tower is connected with the water outlet at the bottom of the negative pressure evaporation tower;
and the gas inlet at the lower part of the ammonia absorption tower is respectively connected with the top gas outlet of the negative pressure evaporation tower and the top gas outlet of the stripping tower.
Further, the ammonia recovery unit also comprises a cooling crystallizer, and water flowing out of a bottom water outlet of the ammonia recovery tower can return to an upper water inlet of the ammonia recovery tower through the cooling crystallizer.
In a preferred embodiment of the invention, the landfill leachate high-efficiency physicochemical deamination pretreatment process comprises the following specific steps:
(1) conveying the landfill leachate to a pretreatment unit to realize solid-liquid separation, and adding 5-15 ppm of a carbonate decomposition auxiliary agent into the supernatant;
(2) conveying the supernatant of the pretreatment unit to a negative pressure evaporation tower of a negative pressure evaporation unit, decomposing carbonate in the supernatant under the conditions that the pressure is-0.06 MPa to-0.1 MPa and the heating temperature is 60-100 ℃ and decomposing carbonate in the supernatant under the help of a carbonate decomposition auxiliary agent so that the pH value of the supernatant is increased to more than 9, then conveying the liquid subjected to negative pressure evaporation to an ammonia stripping unit, wherein the ammonia stripping unit comprises an ammonia stripping tower, the ammonia stripping tower is used for reducing the ammonia nitrogen concentration in the supernatant to be below 200mg/L under the conditions that the gas-liquid ratio is 500-2000:1 and the stripping temperature is 30-60 ℃ so as to enter subsequent biochemical treatment, and conveying the generated gas to an ammonia absorption tower of an ammonia recovery unit;
(3) the method comprises the following steps of conveying gas after ammonia stripping and gas after negative pressure evaporation to an ammonia recovery unit, wherein the ammonia recovery unit comprises an ammonia absorption tower and a cooling crystallizer, ammonia nitrogen in the gas from the negative pressure evaporation tower and the gas from the ammonia stripping tower are absorbed by an ammonia absorption solution through the ammonia absorption tower, the generated gas is discharged after reaching the standard, and the generated liquid is conveyed to the cooling crystallizer for cooling crystallization after the pH value reaches 5-6, and then is filtered and refined to obtain solid ammonium salt.
The invention provides a method and a device for the physicochemical deamination pretreatment of landfill leachate, which have the following beneficial effects:
(1) according to the invention, a small amount of carbonate decomposition auxiliary agent is added and negative pressure evaporation is carried out, so that the decomposition of carbonate contained in the landfill leachate is fully utilized, the pH value of the landfill leachate at the bottom of the tower after the negative pressure evaporation can reach 9-11, higher ammonia nitrogen stripping efficiency can be obtained in the subsequent ammonia nitrogen stripping process without adding alkali, and the treatment cost of ammonia nitrogen removal of the leachate is greatly reduced.
(2) According to the invention, through optimization of an absorption process and an equipment structure, under the conditions that the stripping temperature is 30-60 ℃, the gas-liquid ratio is 500-2000:1 and the pH value is not adjusted by adding alkali, the ammonia nitrogen concentration of the effluent at the bottom of the stripping tower can be reduced to below 200mg/L and can be reduced to dozens of mg/L at least after air stripping, the requirements of subsequent biochemical treatment are completely met, and the treatment cost of denitrification of the landfill leachate is greatly reduced.
(3) On the premise of ensuring that the blow-off tail gas is discharged up to the standard and secondary pollution is avoided, the pregnant solution is cooled and crystallized at the temperature of 20-30 ℃, and solid ammonium salt is directly obtained through filtration and refining, so that the recycling of ammonia nitrogen in the low-energy-consumption wastewater is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and those skilled in the art can also obtain other drawings according to the drawings without creative efforts.
FIG. 1 is a diagram of an apparatus for efficiently pre-treating landfill leachate by deamination according to embodiment 1 of the present invention;
FIG. 2 is a process flow diagram of the high-efficiency physicochemical deamination pretreatment of landfill leachate according to embodiment 2 of the present invention;
wherein:
1: a wastewater adjusting sedimentation tank; 2: a carbonate decomposition auxiliary storage tank; 3: a feed pump; 4: a dosing pump; 5: a flow meter; 6: a waste water heat exchanger; 7: a filler; 8: a distributor; 9: a negative pressure evaporation tower; 10: discharging the water pump; 11: a condenser; 12: a vacuum pump; 13: an effluent-recycle pump; 14: a flow meter; 15: a demister; 16: a stripping tower; 17: an air compressor; 18: a gas flow meter; 19: a heater; 20: an acid absorption liquid circulating pump; 21: an ammonia absorption tower; 22: a heat exchanger; 23: a flow meter; 24: cooling the crystallizer; 25: a filter; 26: and a mother liquor circulating pump.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention,
example 1
Fig. 1 is a diagram of an apparatus for performing high-efficiency physicochemical deamination pretreatment on landfill leachate according to this embodiment, and as shown in fig. 1, the apparatus specifically includes:
(1) a pretreatment unit: the device comprises a wastewater adjusting sedimentation tank 1 and a carbonate decomposition auxiliary agent storage tank 2 which are connected, wherein a feeding pump 3 is arranged on the wastewater adjusting sedimentation tank 1, the carbonate decomposition auxiliary agent storage tank 2 is regulated and controlled by a dosing pump 4, and the effluent of the wastewater adjusting sedimentation tank enters a negative pressure evaporation unit through a flowmeter 5 and a wastewater heat exchanger 6.
(2) A negative pressure evaporation unit: the device comprises a negative pressure evaporation tower 9, wherein a water inlet at the upper part of the negative pressure evaporation tower is connected with a wastewater adjusting sedimentation tank 1, a filler 7 is arranged in the negative pressure evaporation tower, a distributor 8 is arranged, a vacuum pump 12 is arranged outside the negative pressure evaporation tower, a water outlet at the bottom is regulated and controlled by a water outlet pump 10, effluent enters an ammonia stripping unit through a wastewater heat exchanger 6, and gas is discharged to enter an ammonia recovery unit through a condenser 11 under the regulation and control of the vacuum pump 12 through a.
(3) An ammonia stripping unit: the device comprises a stripping tower 16, wherein an upper water inlet of the stripping tower 16 is connected with a bottom water outlet of a negative pressure evaporation tower 9, a demister 15 is arranged inside the stripping tower, the bottom water outlet is regulated and controlled by a water outlet-circulating pump 13, outlet water can be regulated and controlled to enter a subsequent biochemical treatment process or return to the upper water inlet through a flowmeter 14 for circulating stripping, a lower air inlet is regulated and controlled by an air compressor 17 and is provided with a gas flowmeter 18 and a heater 19, and outlet air enters an ammonia recovery unit through a top air outlet of the stripping tower 16.
(4) An ammonia recovery unit: including ammonia recovery tower 21 and cooling crystallizer 24, ammonia recovery tower 21 bottom gas inlet links to each other with negative pressure evaporation tower 9 top gas outlet and the top gas outlet of blow-off tower 16 respectively, ammonia recovery tower 21 bottom delivery port is regulated and control by sour absorption liquid circulating pump 20, can send sour absorption liquid circulation back to ammonia recovery tower 21 upper portion water inlet through flowmeter 23 and heat exchanger 22, or get into cooling crystallizer 24, cooling crystallizer 24 is connected with filter 25, the play water is connected with ammonia recovery tower 21 upper portion water inlet through mother liquor circulating pump 26.
Further, the negative pressure evaporation tower 9 and the stripping tower 16 adopt a packed tower or a plate tower; the foam remover in the tower is one of the foam removers such as a silk screen, a baffle plate and the like; the distributor is one of a double-layer calandria distributor, a nozzle distributor or a shower distributor. The filler of the packed tower is modified pall ring random packing or regular packing; the plate column employs plates with anti-clogging properties.
Example 2
Fig. 2 is a process flow diagram of the embodiment of the efficient physicochemical deamination pretreatment of landfill leachate, and as shown in fig. 2, the process flow mainly includes the following steps:
(1) conveying the landfill leachate to a pretreatment unit to realize solid-liquid separation, and adding a carbonate decomposition auxiliary agent into the supernatant;
(2) and (3) conveying the supernatant of the pretreatment unit to a negative pressure evaporation unit, carrying out negative pressure evaporation until the pH of the supernatant is greater than 9, and conveying the liquid subjected to negative pressure evaporation to an ammonia stripping unit.
(3) And conveying the gas subjected to ammonia stripping and the gas subjected to negative pressure evaporation to an ammonia recovery unit.
Specifically, the specific steps are as follows by combining the equipment diagram of the landfill leachate high-efficiency physicochemical deamination pretreatment shown in fig. 1:
(1) a pretreatment unit: conveying the landfill leachate to a wastewater adjusting sedimentation tank 1 of a pretreatment unit for sedimentation, adding a carbonate decomposition auxiliary agent into the supernatant from a carbonate decomposition auxiliary agent storage tank 2 through a dosing pump 4, wherein the adding amount is 5-15 ppm for promoting the decomposition of carbonate in the landfill leachate, and then exchanging heat of effluent of the landfill leachate at a wastewater heat exchanger 6 and the bottom of a negative pressure evaporation tower 9 to 60-80 ℃ through a flowmeter 5, and feeding the landfill leachate into the negative pressure evaporation tower 9 of a negative pressure evaporation unit.
(2) A negative pressure evaporation unit: the landfill leachate enters a negative pressure evaporation tower 9 and then is uniformly distributed by a distributor 8, and the tower bottom is heated to the temperature of 60-80 ℃; the vacuum pump 12 is used for carrying out negative pressure vacuum pumping in the evaporation tower, the operating pressure is-0.06 MPa to-0.08 MPa, and CO decomposed by carbonate in the landfill leachate2And the gas part containing a large amount of ammonia is condensed by a condenser 11 and then enters the bottom of an ammonia absorption tower of the ammonia absorption unit, and the pH of the liquid part subjected to negative pressure evaporation treatment can be increased to 9-11.
(3) An ammonia stripping unit: the liquid part after negative pressure evaporation and raw water exchange heat and then enter the upper part of a stripping tower 16 and are uniformly distributed by a distributor, the volume ratio of gas to liquid of the stripping tower 16 is regulated and controlled by an air compressor 17, a gas flowmeter 18 and a heater 19 to be 500-2000:1, and the stripping temperature is 30-60 ℃. Pumping the liquid part after stripping into the upper part of a stripping tower 16 through a water outlet-circulating pump 13 and a flowmeter 14 for circular stripping, discharging the landfill leachate after the stripping is finished, and then performing subsequent biochemical treatment, wherein the ammonia nitrogen concentration of the landfill leachate at the moment is reduced to below 200 mg/L. Nitrogen-containing tail gas generated by stripping enters the bottom of an ammonia absorption tower of the ammonia absorption unit through a demister 15; the stripping tower 16 can control the concentration of ammonia nitrogen in the stripping effluent by adjusting the gas-liquid ratio and the circulating amount of wastewater at the bottom of the stripping tower according to requirements.
(4) An ammonia recovery unit: CO generated by the negative pressure evaporation tower 9 and the stripping tower 162And the ammonia-containing mixed tail gas enters the bottom of an ammonia absorption tower 21, acid absorption liquid is pumped into the upper part of the ammonia absorption tower 21 through an acid absorption liquid circulating pump 20 through a flow meter 23 and a heat exchanger 22, and the acid absorption liquid can be one of inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and carbonic acid or organic acids such as citric acidOr several aqueous solutions, the pH is less than 3, the temperature is controlled below 50 ℃, ammonia nitrogen in tail gas is absorbed, and the generated purified gas reaches the standard and is discharged through the tower top. When the pH value of the rich liquid absorbing ammonia at the bottom of the ammonia absorption tower 21 rises to 5-6, pumping out part of the rich liquid to enter a cooling crystallizer 24, cooling to crystallize at 20-30 ℃, cooling to precipitate ammonium salt, filtering and refining to obtain solid ammonium salt, and pumping the mother liquid into the ammonia absorption tower 21 through a mother liquid circulating pump 26.
Example 3
The composition and concentration of certain landfill leachate wastewater are as follows: NH (NH)3N is 1500-2000 mg/L, pH is 8-8.5, and the pretreatment step for removing ammonia nitrogen by using the equipment provided by the invention comprises the following steps:
1) pumping the landfill leachate into a wastewater adjusting sedimentation tank for sedimentation, adding a carbonate decomposition auxiliary agent into the supernatant with the addition of 10ppm, and then exchanging heat with the outlet water of a negative pressure evaporation tower to about 60 ℃.
2) The pretreated wastewater enters the upper part of an evaporation tower and is uniformly distributed by a liquid distributor, and the heating temperature at the bottom of the tower is about 80 ℃; opening a vacuum pump to perform negative pressure vacuum pumping on the evaporation tower, wherein the operation pressure is-0.06 MPa, and the CO decomposed by the carbonate is contained2And the evaporation tail gas of the ammonia enters the bottom of the ammonia absorption tower after being condensed by a demister; after evaporation treatment, the pH value of the garbage percolate at the bottom of the tower is increased to 9.5, and effluent enters the upper part of the stripping tower through a metering pump; the ammonia nitrogen concentration of the effluent after negative pressure evaporation treatment is 440 mg/L.
3) The garbage percolate subjected to negative pressure evaporation treatment enters the upper part of a stripping tower and is uniformly distributed by a liquid distributor, and stripping tail gas containing a large amount of ammonia enters the bottom of an ammonia absorption tower after passing through a demister; wherein the volume ratio of gas to liquid in the process of the stripping tower is 1000:1, the stripping temperature is 35 ℃, and the ammonia nitrogen concentration of the landfill leachate is reduced to 115mg/L after stripping.
4) CO produced by negative pressure evaporation and air stripping process2And the mixed tail gas containing ammonia enters the bottom of the absorption tower, the ammonia is absorbed by 30 percent of sulfuric acid absorption liquid sprayed from the top of the tower, the temperature of the absorption liquid is 45 ℃, and purified gas at the top of the tower is discharged after reaching the standard; when the pH value of the rich solution after ammonia is absorbed at the bottom of the tower is 5.5, the rich solution at the bottom of the absorption tower is pumped into a cooling knot through an absorbent pumpAnd cooling the crystallizer.
5) The rich solution enters a cooling crystallizer, the cooling temperature is 22 ℃, the temperature is reduced to separate out ammonium sulfate crystals, and the ammonium sulfate crystals are obtained through filtration and refining; pumping the mother liquor into an absorption tower for cyclic absorption.
According to the invention, the conditions of negative pressure evaporation and limited negative pressure evaporation are carried out after a small amount of carbonate decomposition auxiliary agent is added, the decomposition of carbonate contained in the landfill leachate is fully utilized, so that the pH value of the landfill leachate at the bottom of the tower is increased to 9.5 after the negative pressure evaporation, and ammonia nitrogen stripping can be carried out without adding alkali; the landfill leachate liquid treated by the landfill leachate materialization deamination pretreatment process provided by the invention is reduced to 115mg/L from 1500-2000 mg/L of ammonia nitrogen content, and completely meets the requirements of subsequent biochemical treatment; the invention directly obtains the solid ammonium salt by optimizing the absorption process and the equipment structure, cooling and crystallizing at 22 ℃, filtering and refining, and has lower energy consumption.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A physicochemical deamination pretreatment method for landfill leachate is characterized by comprising the following steps:
(1) conveying the landfill leachate to a pretreatment unit to realize solid-liquid separation, and adding a carbonate decomposition auxiliary agent into the supernatant;
(2) and (3) conveying the supernatant of the pretreatment unit to a negative pressure evaporation unit, carrying out negative pressure evaporation until the pH of the supernatant is greater than 9, and conveying the liquid subjected to negative pressure evaporation to an ammonia stripping unit.
2. The landfill leachate physicochemical deamination pretreatment method of claim 1, further comprising:
(3) and conveying the gas subjected to ammonia stripping and the gas subjected to negative pressure evaporation to an ammonia recovery unit.
3. The landfill leachate physicochemical deamination pretreatment method according to claim 1 or 2, wherein the negative pressure evaporation unit in the step (2) comprises a negative pressure evaporation tower, and the operating pressure of the negative pressure evaporation tower is-0.1 MPa to-0.06 MPa, preferably-0.08 MPa to-0.06 MPa when negative pressure evaporation is performed; the heating temperature is 60 ℃ to 100 ℃, preferably 60 ℃ to 80 ℃.
4. The landfill leachate physicochemical deamination pretreatment method according to claim 3, wherein the negative pressure evaporation tower is any one of a packed tower or a plate tower; the packed tower adopts anti-blocking random packing, preferably takes pall rings as base materials and carries out anti-blocking modification on the surface of the base materials; the plate tower adopts an anti-blocking tower plate.
5. The landfill leachate physicochemical deamination pretreatment method as claimed in claim 2, wherein the ammonia stripping unit in step (2) comprises a stripping tower, wherein the gas-liquid ratio in the stripping tower is 500-2000:1, the stripping temperature is 30-60 ℃, and the generated tail gas is delivered to the ammonia recovery unit.
6. The method for pre-treating the landfill leachate by the physicochemical deamination according to the claim 2, wherein the ammonia recovery unit in the step (3) comprises an ammonia absorption tower, and the ammonia absorption solution is an aqueous solution of an organic acid and/or an inorganic acid, wherein the inorganic acid is preferably sulfuric acid, hydrochloric acid, phosphoric acid or carbonic acid, and the organic acid is preferably citric acid; the ammonia absorbing solution has a pH of less than 3.
7. The landfill leachate physicochemical deamination pretreatment method of claim 6, wherein the absorption temperature in the ammonia absorption tower is 40-50 ℃.
8. The method for pre-treating the landfill leachate by the physicochemical deamination according to the claim 6 or 7, wherein the ammonia recovery unit further comprises a cooling crystallizer, and when the rich solution after ammonia absorption in the ammonia absorption tower is close to saturation, the rich solution is conveyed to the cooling crystallizer.
9. The landfill leachate physicochemical deamination pretreatment method according to claim 8, wherein the cooling crystallizer filters and refines crystals precipitated by cooling at a cooling temperature of 20-30 ℃, and the mother liquor is delivered to the ammonia absorption tower; the cooling temperature is preferably 22 ℃.
10. The utility model provides a landfill leachate materialization deamination preliminary treatment equipment which characterized in that includes: the device comprises a pretreatment unit, a negative pressure evaporation unit, an ammonia stripping unit and an ammonia recovery unit; wherein,
the pretreatment unit comprises a wastewater adjusting sedimentation tank and a carbonate decomposition auxiliary agent storage tank which are connected, the negative pressure evaporation unit comprises a negative pressure evaporation tower, the ammonia stripping unit comprises a stripping tower, and the ammonia recovery unit comprises an ammonia absorption tower; wherein,
the water inlet at the upper part of the negative pressure evaporation tower is connected with the water outlet of the wastewater adjusting sedimentation tank;
the water inlet at the upper part of the stripping tower is connected with the water outlet at the bottom of the negative pressure evaporation tower;
and the gas inlet at the lower part of the ammonia absorption tower is respectively connected with the top gas outlet of the negative pressure evaporation tower and the top gas outlet of the stripping tower.
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Application publication date: 20191025 |