CN113105138A - Method and system for water washing dechlorination of waste incineration fly ash and evaporation mass-separation crystallization of water washing liquid - Google Patents
Method and system for water washing dechlorination of waste incineration fly ash and evaporation mass-separation crystallization of water washing liquid Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 268
- 239000010881 fly ash Substances 0.000 title claims abstract description 211
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 238000005406 washing Methods 0.000 title claims abstract description 146
- 238000001704 evaporation Methods 0.000 title claims abstract description 105
- 230000008020 evaporation Effects 0.000 title claims abstract description 101
- 238000002425 crystallisation Methods 0.000 title claims abstract description 94
- 230000008025 crystallization Effects 0.000 title claims abstract description 94
- 238000000926 separation method Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004056 waste incineration Methods 0.000 title claims abstract description 24
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 10
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 137
- 238000010828 elution Methods 0.000 claims abstract description 125
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 93
- 238000004537 pulping Methods 0.000 claims abstract description 82
- 239000002002 slurry Substances 0.000 claims abstract description 70
- 239000001103 potassium chloride Substances 0.000 claims abstract description 69
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 68
- 239000011780 sodium chloride Substances 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 41
- 239000010802 sludge Substances 0.000 claims abstract description 40
- 239000011552 falling film Substances 0.000 claims abstract description 38
- 239000012528 membrane Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 31
- 238000001728 nano-filtration Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000007791 liquid phase Substances 0.000 claims description 104
- 239000007790 solid phase Substances 0.000 claims description 37
- 238000001556 precipitation Methods 0.000 claims description 34
- 239000011575 calcium Substances 0.000 claims description 33
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 32
- 238000005189 flocculation Methods 0.000 claims description 32
- 230000016615 flocculation Effects 0.000 claims description 31
- 239000012452 mother liquor Substances 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 29
- 239000006228 supernatant Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 229910052791 calcium Inorganic materials 0.000 claims description 21
- 239000011777 magnesium Substances 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 238000000746 purification Methods 0.000 claims description 20
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 12
- 239000012267 brine Substances 0.000 claims description 12
- 229910001424 calcium ion Inorganic materials 0.000 claims description 12
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 12
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000003814 drug Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000010413 mother solution Substances 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims 2
- 238000009413 insulation Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000428 dust Substances 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000382 dechlorinating effect Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 238000011268 retreatment Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method and a system for water washing dechlorination of waste incineration fly ash and evaporation mass-separation crystallization of water washing liquid. The method comprises the following steps: the method comprises the following steps of (1) pulping waste incineration fly ash, and then carrying out multi-stage elution to obtain washing fly ash and washing liquid; purifying the water washing solution to obtain clear liquid and precipitated slurry; adjusting the pH value of the clear liquid to obtain an evaporation raw material liquid, and sequentially carrying out preheating, falling film heat exchange, forced circulation heat exchange, evaporation crystallization treatment, sodium chloride crystallization separation, nanofiltration membrane treatment and potassium chloride crystallization separation to obtain potassium chloride and sodium chloride products; and (3) desliming the precipitated slurry to obtain sludge and clear liquid, and drying the sludge and the washed fly ash to obtain fly ash. The invention adopts multi-stage countercurrent and alkaline water washing technologies, has low water consumption, no dust emission, good dechlorination effect and low heavy metal leaching rate; divalent ions in the feed liquid are intercepted by adopting a nanofiltration membrane treatment technology, the quality of the crystallized salt is effectively improved, the long-term stable operation of the system can be ensured, and the cyclic utilization and zero discharge of process water are realized while the consumption of clear water is reduced.
Description
Technical Field
The invention relates to a method and a system for treating waste incineration fly ash, in particular to a method and a system for water washing dechlorination and water washing liquid evaporation mass-separation crystallization of waste incineration fly ash, belonging to the field of retreatment and utilization of waste incineration fly ash.
Background
The waste incineration fly ash is a powdery substance which is collected in a flue gas pipeline, a flue gas purification device, a separator, a dust remover device and the like in the waste incineration process and has light volume weight and small particle size, and the total amount accounts for 3-5% of the treatment amount of the household waste. At present, the technology of cooperatively treating fly ash by adopting a cement kiln is an effective technical means for realizing harmless, reduction and resource treatment of waste incineration fly ash. However, a large amount of substances such as chlorine, potassium, sodium and the like in the fly ash can affect the quality of clinker and the quality of cement and easily cause the crust in the kiln. The water washing pretreatment can transfer soluble substances (potassium, sodium and chloride ions) in the fly ash into water washing liquid, the fly ash water washing liquid contains about 6 wt% -15 wt% of potassium and sodium salts, potassium salts and sodium salts are prepared from the fly ash water washing liquid through an evaporation crystallization technology, and the vacancy of the potassium salts is relieved.
The content of sodium salt in the existing fly ash water washing liquid is higher than that of potassium salt, the high-content sodium salt is crystallized and separated out by utilizing the principle of high-temperature sodium precipitation and low-temperature potassium precipitation in an evaporation crystallization process, then the mother liquor is continuously refluxed to enrich the potassium salt, the potassium salt can be separated out after being cooled and cooled after being saturated, and the obtained mixed salt of the sodium salt and the potassium salt is obtained without separation.
The Chinese invention patent (CN 105478438A) discloses a method for co-processing and harmless resource recycling of a garbage fly ash cement kiln, which comprises a three-stage washing and desalting process; a process for removing heavy metal by coagulating sedimentation; membrane distillation concentration process; removing extremely trace impurity salt; triple effect evaporation crystallization process. The third-stage washing desalination process is to remove chloride ions in the fly ash under the action of water and a dissolution promoter to obtain a solution containing the chloride ions and the fly ash containing less than 1% of the chloride ions; the technology for removing heavy metal by coagulating sedimentation can remove various metal ions in the fly ash, and the precipitate is pre-dried and then enters a cement kiln for incineration; the membrane distillation concentration process can remove the rest chloride ions in the solution and the generated distilled water can be recycled; the process for removing the extremely trace impurity salt can remove the extremely trace impurity salt and recycle heat energy; the triple effect evaporation crystallization process is used for evaporating and separating the high salt-containing concentrated solution to obtain industrial salt for the papermaking process, the snow-melting agent and the chlor-alkali industry. The method realizes harmless and resource treatment of the fly ash to a certain extent, the waste incineration fly ash can meet the raw material standard for cement production, redundant chloride ions in the solution can be removed by utilizing a membrane distillation concentration process, the produced distilled water can be recycled, and extremely trace impurity salts can be removed by adopting an extremely trace impurity salt removal process. However, in the three-stage water washing desalination process, the addition of the dissolution promoting agent for three times and the consumption of a large amount of water cause resource waste and cost increase; the miscellaneous salt obtained by the extremely-trace miscellaneous salt removing process belongs to dangerous waste, and is buried or burned and is treated according to the standard of the dangerous waste; finally, the purity of the obtained salt product is only over 70 percent, and the salt quality is lower. Therefore, the above-mentioned defects existing in the harmless resource recycling method of the waste fly ash in the prior art are in urgent need of improvement.
Disclosure of Invention
One purpose of the invention is to provide a treatment method for dechlorinating waste incineration fly ash by water washing and evaporating and crystallizing water washing liquid according to quality;
one of the purposes of the invention is to provide a treatment system for realizing the treatment method of the waste incineration fly ash water washing dechlorination and the water washing liquid evaporation dual crystallization;
the above object of the present invention is achieved by the following technical solutions:
the invention firstly provides a treatment method for water washing dechlorination and water washing liquid evaporation mass-separation crystallization of waste incineration fly ash, which comprises the following steps: (1) stirring the waste incineration fly ash and pulping water to prepare fly ash slurry; (2) performing multi-stage elution on the fly ash slurry by using water to obtain water-washed fly ash and water-washed liquid; (3) purifying the water washing liquid to obtain clear liquid and precipitated slurry; adjusting the pH value of the clear liquid to obtain an evaporation raw material liquid; (4) sequentially carrying out preheating treatment, falling film heat exchange treatment, forced circulation heat exchange treatment, evaporation crystallization treatment, sodium chloride crystallization separation treatment, nanofiltration membrane treatment and potassium chloride crystallization separation treatment on the evaporation raw material liquid to obtain potassium chloride and sodium chloride products; (5) carrying out desliming treatment on the precipitated slurry obtained in the step (3) to obtain sludge and clear liquid; and (3) drying the sludge and the water-washed fly ash generated in the step (2) to obtain a fly ash finished product.
In a preferred embodiment of the present invention, the mass ratio of the waste incineration fly ash to the pulping water in step (1) is preferably 1:2-1:4, and most preferably 1: 3.
As a preferred embodiment of the present invention, the multi-stage elution in the step (2) is preferably a three-stage elution; specifically, the fly ash slurry prepared in the step (1) enters a first-stage elution separation device to carry out first-stage elution to obtain first-stage washing fly ash and first-stage washing liquid; mixing the first-stage washing fly ash with pulping water to obtain first-stage fly ash slurry, and allowing the first-stage fly ash slurry to enter a second-stage elution separation device for second-stage elution to obtain second-stage washing fly ash and second-stage washing liquid; mixing the second-stage water-washing fly ash with pulping water to obtain second-stage fly ash slurry, and performing third-stage elution on the second-stage fly ash slurry in a third-stage elution separation device to obtain third-stage water-washing fly ash and third-stage water-washing liquid; wherein, the water content of the water washing fly ash obtained in each stage of elution step is not more than 40 percent, and the solid content of the water washing liquid is lower than 1 percent; finally, drying the three-level washing fly ash to obtain a fly ash finished product, for example, drying the three-level washing fly ash by adopting steam or hot air as a drying medium to obtain a fly ash finished product; wherein the temperature of the drying medium is preferably below 300 ℃, most preferably 160-260 ℃; the water content of the obtained fly ash finished product is lower than 5 percent.
As a more preferable embodiment of the invention, the secondary water washing solution is used as the water for pulping in the step (1), and the tertiary water washing solution is used as the pulping water in the secondary elution; the circulating water and the makeup water of the process are used as the pulping water for the third-stage elution, and the clear water is used as the pulping water for the third-stage elution during the initial work.
As a more preferable specific embodiment of the present invention, in the step (3), the first-stage water washing liquid in the step (2) is adopted to perform purification treatment to obtain clear liquid and precipitated slurry, wherein the purification treatment sequentially comprises calcium and magnesium ion removal, heavy metal removal, flocculation precipitation treatment and multi-stage filtration treatment to finally obtain the clear liquid and the precipitated slurry.
As a more preferable embodiment of the present invention, the calcium and magnesium ion removal may be a calcium and magnesium ion removal treatment by adding sodium carbonate with a certain mass concentration to a calcium and magnesium ion removal device; the heavy metal removal treatment can be that a heavy metal trapping agent (sodium sulfide, sodium thiosulfate and a special medicament) is added into a heavy metal removal device to carry out heavy metal removal treatment; the flocculation precipitation treatment can be that a flocculation precipitation medicament is added for flocculation precipitation reaction; the multistage filtration treatment can be filtration sequentially through filtration membranes with filtration pore diameters of 10 μm, 5 μm and 1 μm; the pH value is adjusted to 6-8 by using an acidic solution.
As a preferred embodiment of the present invention, the preheating treatment in the step (4) is to preheat the evaporation raw material liquid at a temperature of 80 ℃ to 110 ℃; the falling film heat exchange treatment can be heating evaporation of preheated feed liquid in a falling film heat exchanger, wherein the temperature in the falling film heat exchanger is controlled to be 80-100 ℃, the feed liquid is circularly heated and evaporated in the falling film heat exchanger, when the solid-to-liquid ratio in the feed liquid reaches 20-25%, the feed liquid enters a forced circulation heat exchanger for forced circulation heat exchange treatment, the temperature of the forced circulation heat exchanger is controlled to be 90-120 ℃, the feed liquid is evaporated and concentrated, the feed liquid (the solid-to-liquid ratio is more than or equal to 30%) obtained after evaporation and concentration enters an evaporation crystallizer, and crystal slurry and concentrated brine with the salt content of 30-60 wt% are obtained after crystallization and layering in the evaporation crystallizer; conveying the strong brine to a forced circulation heat exchanger for continuous evaporation and concentration, allowing the crystal slurry to enter a sodium chloride crystallization separator for crystallization to obtain crystallized salt and feed liquid, and separating the crystallized salt and the feed liquid to obtain sodium chloride crystallized salt with the water content of not more than 6 wt%, supernatant and sodium chloride mother liquor; sending the supernatant to a nanofiltration treatment device when the supernatant reaches a potassium chloride saturated solution, treating the supernatant to obtain a clear solution and a concentrated solution, returning the concentrated solution to a fly ash elution unit, sending the clear solution to a potassium chloride crystallization separator for cooling, separating the crystallized salt from the feed solution when the temperature is reduced to 10-50 ℃ and crystals are separated out, and obtaining potassium chloride crystallized salt with the water content of not more than 6 wt%, a potassium chloride mother solution and a non-crystallized potassium chloride mother solution; discharging the non-crystallized potassium chloride mother liquor to a fly ash elution unit for elution treatment; and conveying the sodium chloride mother liquor and the potassium chloride mother liquor to a forced circulation heat exchanger for evaporation and concentration treatment.
As a preferred embodiment of the invention, condensed water (with the temperature of 80-100 ℃) generated in the falling film heat exchange treatment and forced circulation heat exchange treatment processes is used for preheating water in the multi-stage preheating process;
as a preferred embodiment of the present invention, the condensed water produced in the multi-stage preheating process is used as the water for pulp making during the elution of fly ash.
In a preferred embodiment of the invention, the nanofiltration membrane treatment device is provided with an insulating layer, so that the supernatant entering the device is not cooled to separate out crystals.
As a preferred embodiment of the present invention, the clear solution described in the step (5) is repeatedly subjected to the treatment steps (3) to (5).
The above-described process can be carried out by those skilled in the art using various conventional apparatuses for fly ash treatment and reuse, which are easily implemented by those skilled in the art.
The invention further provides a treatment system for realizing the treatment method of the waste incineration fly ash water washing dechlorination and the water washing liquid evaporation dual crystallization, wherein the treatment system comprises a fly ash pulping unit, a fly ash elution unit, a water washing liquid purification unit, an evaporation crystallization unit and a drying unit; the fly ash washing unit is provided with a fly ash slurry inlet, a solid-phase product outlet, a liquid-phase product outlet and a pulping water inlet; the washing liquid purification unit is provided with a liquid phase inlet, a liquid phase outlet and a solid phase outlet; the evaporative crystallization unit is provided with an evaporative raw material liquid inlet, a non-crystallization mother liquid outlet and a condensed water outlet;
the device comprises a fly ash pulping unit, a fly ash washing unit, a drying unit, a water washing liquid purifying unit, a fly ash pulp outlet of the fly ash pulping unit, a fly ash pulp inlet of the fly ash washing unit, a solid-phase product outlet of the fly ash washing unit, a liquid-phase inlet of the water washing liquid purifying unit, a liquid-phase outlet of the water washing liquid purifying unit, an evaporation raw material liquid inlet of the evaporation crystallization unit, a solid-phase outlet of the water washing liquid purifying unit, an inlet of the drying unit, an outlet of non-crystallization mother liquid of the evaporation crystallization unit, a liquid-phase inlet of the water washing liquid purifying unit and a condensed water outlet of the evaporation crystallization unit, wherein the fly ash pulp inlet of the fly ash washing unit is.
As a preferred embodiment of the present invention, the fly ash pulping unit may include a fly ash metering device, a pulping water metering device, and a pulping apparatus; the fly ash metering device is provided with a fly ash inlet and a fly ash outlet, the pulping water metering device is provided with a pulping water inlet and a pulping water outlet, the pulping equipment is provided with a fly ash feeding hole, a pulping water inlet and a fly ash slurry outlet, wherein the fly ash outlet of the fly ash metering device is connected with the fly ash feeding hole of the pulping equipment, and the pulping water outlet of the pulping water metering device is connected with the pulping water inlet of the pulping equipment.
As a preferred embodiment of the present invention, the fly ash elution unit comprises a primary elution separation device, a secondary elution separation device and a tertiary elution separation device; wherein the first-stage elution separation device is provided with a fly ash slurry inlet, a water washing liquid outlet and a solid phase outlet; the second-stage elution separation device is provided with a slurry inlet, a solid-phase outlet and a liquid-phase inlet; the three-stage elution separation device is provided with a slurry inlet, a solid phase outlet and a liquid phase outlet; wherein, one-level elution separator's wash solution export with wash solution purification unit's wash solution entry link to each other, one-level elution separator's solid phase export with second grade elution separator's thick liquid entry link to each other, second grade elution separator's liquid phase export with the entry of the process water metering device of slurrying unit link to each other, second grade elution separator's solid phase export with third grade elution separator's thick liquid entry link to each other, third grade elution separator's liquid phase export with second grade elution separator's liquid phase entry link to each other, third grade elution separator's solid phase export the entry of drying unit links to each other.
As a preferred embodiment of the present invention, the washing liquid purification unit may include a calcium and magnesium removal device, a heavy metal removal device, a flocculation precipitation device, a multi-stage filtration device, a desliming device, and a pH adjustment device; the calcium and magnesium removing device is provided with a washing liquid inlet, a liquid phase outlet and a sludge outlet; the heavy metal removal device is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the flocculation precipitation device is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the multistage filtering device is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the pH value adjusting device is provided with a liquid phase inlet and a liquid phase outlet; the desliming device is provided with a sludge inlet, a solid phase outlet and a liquid phase outlet; the device comprises a fly ash elution unit, a calcium magnesium removal device, a heavy metal removal device, a flocculation precipitation device, a multi-stage filtration device and a pH value adjustment device, wherein a washing liquid inlet of the calcium magnesium removal device is connected with a liquid phase outlet of a first-stage elution separation device of the fly ash elution unit, a liquid phase outlet of the calcium magnesium removal device is connected with a liquid phase inlet of the heavy metal removal device, a liquid phase outlet of the heavy metal removal device is connected with a liquid phase inlet of the flocculation precipitation device, a liquid phase outlet of the flocculation precipitation device is connected with a liquid phase inlet of the multi-stage filtration device, and a liquid; the sludge outlet of the calcium and magnesium removal device, the sludge outlet of the heavy metal removal device, the sludge outlet of the flocculation precipitation device and the sludge outlet of the multistage filtering device are all connected with the sludge inlet of the desliming device; the solid phase outlet of the desliming device is connected with the inlet of the drying unit, the solid phase outlet of the desliming device is connected with the drying unit, the liquid phase outlet of the desliming device is connected with the washing liquid inlet of the calcium and magnesium removing device, and the liquid phase outlet of the pH value adjusting device is connected with the inlet of the evaporative crystallization unit.
As a preferred embodiment of the invention, the evaporative crystallization unit comprises a multi-stage preheater, a falling film heat exchanger, a forced circulation heat exchanger, an evaporative crystallizer, a sodium chloride crystallization separator, a nanofiltration membrane treatment device and a potassium chloride crystallization separator; the multi-stage preheater is provided with an evaporation raw material liquid inlet, a preheating water inlet, a condensed water outlet and a liquid phase outlet; the falling film heat exchanger is provided with a feed liquid inlet, a condensed water outlet and an evaporated liquid outlet; the forced circulation heat exchanger is provided with a feed liquid inlet, a condensed water outlet and an evaporated liquid outlet; the evaporation crystallizer is provided with an evaporation liquid inlet, a crystal slurry outlet and a strong brine outlet; the sodium chloride crystallization separator is provided with a crystal slurry inlet, a sodium chloride crystallized salt outlet, a supernatant outlet and a mother liquor outlet; the nanofiltration membrane treatment device is provided with a supernatant inlet, a clear liquid outlet and a concentrated liquid outlet; the potassium chloride crystallization separator is provided with a clear liquid inlet, a potassium chloride crystallized salt outlet, a potassium chloride mother liquid outlet and a potassium chloride mother liquid outlet which does not crystallize;
wherein an evaporation raw material liquid inlet of the multi-stage preheater is connected with a liquid phase outlet of a pH value adjusting device of the washing liquid purifying unit; a liquid phase outlet of the multi-stage preheater is connected with a feed liquid inlet of the falling film heat exchanger, and an evaporation liquid outlet of the falling film heat exchanger is connected with a feed liquid inlet of the forced circulation heat exchanger; an evaporation liquid outlet of the forced circulation heat exchanger is connected with an evaporation liquid inlet of the evaporation crystallizer, a condensed water outlet of the falling film heat exchanger and a condensed water outlet of the forced circulation heat exchanger are connected with a preheating water inlet of the multi-stage preheater, a crystal slurry outlet of the evaporation crystallizer is connected with a crystal slurry inlet of the sodium chloride separator, and a strong brine outlet of the evaporation crystallizer is connected with a feed liquid inlet of the forced circulation heat exchanger; a sodium chloride mother liquor outlet of the sodium chloride separator is connected with a feed liquid inlet of the forced circulation heat exchanger through a mother liquor return pipeline, and a supernatant outlet of the sodium chloride separator is connected with a supernatant inlet of the nanofiltration membrane treatment device; a clear liquid outlet of the nanofiltration membrane treatment device is connected with a clear liquid inlet of the potassium chloride crystal separator; a potassium chloride mother liquor outlet of the potassium chloride crystallization separator is connected with a feed liquid inlet of the forced circulation heat exchanger,
and a concentrated solution outlet of the nanofiltration membrane treatment device and a non-crystallized potassium chloride mother solution outlet of the potassium chloride crystallization separator are connected with an inlet of the fly ash elution unit.
Compared with the prior art, the invention has the following advantages and prominent technical effects:
1. the fly ash elution unit adopts multi-stage countercurrent and alkaline water washing technologies, so that the water consumption is low, no dust is raised, the dechlorination effect is good, and the heavy metal leaching rate is low.
2. The nanofiltration membrane treatment technology is adopted to intercept divalent ions in the feed liquid and improve the quality of potassium salt.
3. The non-crystallization mother liquor generated by the evaporation crystallization unit is recycled to the fly ash elution unit, so that the consumption of forced circulation evaporation equipment is reduced to a certain extent, the quality of crystallized salt is improved, and the long-term stable operation of the system is ensured.
4. The recycling of the concentrated liquid and the mother liquid which is not crystallized after the FWD process, the condensed water and the nanofiltration treatment reduces the consumption of clear water in the fly ash elution unit and realizes the recycling and zero emission of process water.
Drawings
FIG. 1 is a process flow diagram of the process of the present invention.
FIG. 2 is a schematic diagram of the components and connections of the devices in the system of the present invention.
Reference numerals: the method comprises the following steps of 1-fly ash metering device, 2-fly ash water metering device, 3-fly ash pulping device, 4-first-stage elution separation device, 5-second-stage elution separation device, 6-third-stage elution separation device, 7-calcium and magnesium removal device, 8-heavy metal removal device, 9-flocculation precipitation device, 10-multistage filtration device, 11-desliming device, 12-pH adjusting device, 13-multistage preheater, 14-falling film heat exchanger, 15-forced circulation heat exchanger, 16-evaporation crystallizer, 17-sodium chloride crystallization separator, 18-nanofiltration treatment device and 19-potassium chloride crystallization separator.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. It is to be understood that the described embodiments are exemplary only and are not limiting upon the scope of the invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be within the scope of the invention.
In the description of the embodiments of the present application, it should be noted that the indication of orientation or positional relationship is based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship which is usually placed when the product of the application is used, or the orientation or positional relationship which is usually understood by those skilled in the art, or the orientation or positional relationship which is usually placed when the product of the application is used, and is only for the convenience of describing the application and simplifying the description, but does not indicate or imply that the indicated device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the application. In the description of the embodiments of the present application, it should also be noted that, unless otherwise explicitly stated or limited, the terms "disposed," "mounted," and "connected" are to be construed broadly, and may for example be fixedly connected, detachably connected, or integrally connected; may be directly connected or indirectly connected through an intermediate. The specific meaning of the above terms in the present application can be understood in a specific case by those of ordinary skill in the art.
In the description of embodiments of the present application, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Referring to fig. 1, the invention provides a treatment method for dechlorinating waste incineration fly ash by water washing and evaporating and crystallizing water washing liquid according to quality, which comprises the following steps: (1) stirring the waste incineration fly ash and pulping water to prepare fly ash slurry; (2) carrying out multi-stage elution on the fly ash slurry by using water to obtain water-washed fly ash and water-washed liquid; (3) purifying the water washing liquid to obtain clear liquid and precipitated slurry; adjusting the pH value of the clear liquid to obtain an evaporation raw material liquid; (4) sequentially carrying out preheating treatment, falling film heat exchange treatment, forced circulation heat exchange treatment, evaporation crystallization treatment, sodium chloride crystallization separation treatment, nanofiltration membrane treatment and potassium chloride crystallization separation treatment on the evaporation raw material liquid to obtain potassium chloride and sodium chloride products; (5) carrying out desliming treatment on the precipitated slurry obtained in the step (3) to obtain sludge and clear liquid; and (3) drying the sludge and the water-washed fly ash generated in the step (2) to obtain a fly ash finished product.
In a preferred embodiment of the present invention, the mass ratio of the waste incineration fly ash to the pulping water in step (1) is preferably 1:2 to 1:4, and most preferably 1: 3.
As a preferred embodiment of the present invention, the multi-stage elution in the step (2) is a three-stage elution; preferably, the tertiary elution comprises: putting the fly ash slurry prepared in the step (1) into a primary elution separation device for primary elution to obtain primary washing fly ash and primary washing liquid; mixing the first-stage washing fly ash with pulping water to obtain first-stage fly ash slurry, and allowing the first-stage fly ash slurry to enter a second-stage elution separation device for second-stage elution to obtain second-stage washing fly ash and second-stage washing liquid; mixing the second-stage water-washing fly ash with pulping water to obtain second-stage fly ash slurry, and performing third-stage elution on the second-stage fly ash slurry in a third-stage elution separation device to obtain third-stage water-washing fly ash and third-stage water-washing liquid; drying the three-stage washing fly ash to obtain a fly ash finished product; more preferably, the secondary water washing liquid is used as the pulping water in the step (1), and the tertiary water washing liquid is used as the pulping water in the second-stage elution; circulating water and makeup water are used as pulping water for the third-stage elution, and clear water is used as the pulping water for the third-stage elution during initial work.
As a preferred specific embodiment of the invention, in the step (3), the first-stage water washing liquid in the step (2) is adopted for purification treatment to obtain clear liquid and precipitated slurry, wherein the purification treatment sequentially comprises calcium and magnesium ion removal, heavy metal removal, flocculation precipitation treatment and multi-stage filtration treatment to finally obtain the clear liquid and the precipitated slurry; further preferably, the calcium and magnesium ion removal is to add sodium carbonate into a calcium and magnesium ion removal device to perform calcium and magnesium ion removal treatment; the heavy metal removal treatment is to add a heavy metal catching agent into a heavy metal removal device to carry out heavy metal removal treatment; the flocculation precipitation treatment is to add a flocculation precipitation medicament for flocculation precipitation reaction; the multistage filtration treatment is to sequentially filter by filtration membranes with the filtration pore diameters of 10 microns, 5 microns and 1 micron; the pH value is adjusted to 6-8 by using an acidic solution.
As a preferred embodiment of the present invention, the preheating treatment in the step (4) is to preheat the evaporation raw material liquid at a temperature of 80 ℃ to 110 ℃; the falling film heat exchange treatment comprises the steps of feeding preheated feed liquid into a falling film heat exchanger for heating evaporation, wherein the temperature in the falling film heat exchanger is controlled to be 80-100 ℃, the feed liquid is circularly heated and evaporated in the falling film heat exchanger, the feed liquid enters a forced circulation heat exchanger for forced circulation heat exchange treatment when the solid-to-liquid ratio in the feed liquid reaches 20-25%, the temperature of the forced circulation heat exchanger is controlled to be 90-120 ℃, the feed liquid is evaporated and concentrated, the feed liquid obtained after evaporation and concentration enters an evaporation crystallizer, and crystal slurry and concentrated brine are obtained after crystallization and layering in the evaporation crystallizer; conveying the strong brine to a forced circulation heat exchanger for continuous evaporation and concentration, introducing the crystal slurry into a sodium chloride crystallization separator for crystallization to obtain crystallized salt and feed liquid, and separating the crystallized salt and the feed liquid to obtain sodium chloride crystallized salt, supernatant and sodium chloride mother liquor; when the supernatant reaches a potassium chloride saturated solution, sending the supernatant into a nanofiltration membrane treatment device, and treating to obtain a clear liquid and a concentrated liquid; carrying out multi-stage elution on the concentrated solution to obtain washing fly ash and washing liquid; the clear liquid enters a potassium chloride crystallization separator to be cooled and crystallized to obtain crystallized salt and feed liquid, and the crystallized salt and the feed liquid are separated to obtain potassium chloride crystallized salt, potassium chloride mother liquid and non-crystallized potassium chloride mother liquid; carrying out multi-stage elution treatment on the potassium chloride mother liquor which is not crystallized to obtain washing fly ash and washing liquor; and conveying the sodium chloride mother liquor and the potassium chloride mother liquor to a forced circulation heat exchanger for evaporation and concentration treatment.
As a preferred embodiment of the invention, the condensed water produced in the falling film heat exchange treatment and forced circulation heat exchange treatment is used as the preheating water in the multi-stage preheating process; and the condensed water generated in the multi-stage preheating process is used as water for pulping when the fly ash is eluted.
Referring to fig. 2, the present invention further provides a system for implementing the above-mentioned treatment method, the system comprises a fly ash pulping unit, a fly ash elution unit, a water washing liquid purification unit, an evaporative crystallization unit and a drying unit; the fly ash pulp making unit is provided with a fly ash pulp outlet, and the fly ash eluting unit is provided with a fly ash pulp inlet, a solid-phase product outlet, a liquid-phase product outlet and a pulp making water inlet; the washing liquid purification unit is provided with a liquid phase inlet, a liquid phase outlet and a solid phase outlet; the evaporative crystallization unit is provided with an evaporative raw material liquid inlet, a non-crystallization mother liquid outlet and a condensed water outlet;
the device comprises a fly ash pulping unit, a fly ash washing unit, a drying unit, a water washing liquid purifying unit, a fly ash pulp outlet of the fly ash pulping unit, a fly ash pulp inlet of the fly ash washing unit, a solid-phase product outlet of the fly ash washing unit, a liquid-phase inlet of the water washing liquid purifying unit, a liquid-phase outlet of the water washing liquid purifying unit, an evaporation raw material liquid inlet of the evaporation crystallization unit, a solid-phase outlet of the water washing liquid purifying unit, an inlet of the drying unit, an outlet of non-crystallization mother liquid of the evaporation crystallization unit, a liquid-phase inlet of the water washing liquid purifying unit and a condensed water outlet of the evaporation crystallization unit, wherein the fly ash pulp inlet of the fly ash washing unit is.
As a preferred embodiment of the invention, the fly ash pulping unit comprises a fly ash metering device 1, a pulping water metering device 2 and a pulping device 3; the fly ash metering device 1 is provided with a fly ash inlet and a fly ash outlet, the pulping water metering device 2 is provided with a pulping water inlet and a pulping water outlet, and the pulping equipment 3 is provided with a fly ash feeding port, a pulping water inlet and a fly ash pulp outlet, wherein the fly ash outlet of the fly ash metering device 1 is connected with the fly ash feeding port of the pulping equipment 3, and the pulping water outlet of the pulping water metering device 2 is connected with the pulping water inlet of the pulping equipment 3.
As a preferred embodiment of the present invention, the fly ash elution unit comprises a primary elution separation device 4, a secondary elution separation device 5, and a tertiary elution separation device 6; the first-stage elution separation device 4 is provided with a fly ash slurry inlet, a water washing liquid outlet and a solid phase outlet; the second-stage elution separation device 5 is provided with a slurry inlet, a solid-phase outlet and a liquid-phase inlet; the third-stage elution separation device 6 is provided with a slurry inlet, a solid-phase outlet and a liquid-phase outlet; wherein, the wash liquor export of one-level elution separator 4 with wash liquor purification unit's wash liquor entry link to each other, the solid phase export of one-level elution separator 4 with second grade elution separator 5's thick liquid entry link to each other, the liquid phase export of second grade elution separator (5) with the slurrying water metering device 2's of slurrying unit slurrying water import link to each other, second grade elution separator 5's solid phase export with third grade elution separator 6's thick liquid entry link to each other, third grade elution separator 6's liquid phase export with second grade elution separator 5's liquid phase entry link to each other, third grade elution separator 6's solid phase export the entry of drying unit links to each other.
As a preferred embodiment of the invention, the washing liquid purification unit comprises a calcium and magnesium removal device 7, a heavy metal removal device 8, a flocculation precipitation device 9, a multi-stage filtration device 10, a desliming device 11 and a pH value adjustment device 12; the calcium and magnesium removing device 7 is provided with a washing liquid inlet, a liquid phase outlet and a sludge outlet; the heavy metal removal device 8 is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the flocculation precipitation device 9 is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the multistage filtering device 10 is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the desliming device 11 is provided with a sludge inlet, a solid phase outlet and a liquid phase outlet; the pH value adjusting device 12 is provided with a liquid phase inlet and a liquid phase outlet; wherein, the water washing liquid inlet of the calcium and magnesium removing device 7 is connected with the liquid phase outlet of the first-stage elution separation device 4 of the fly ash elution unit, the liquid phase outlet of the calcium and magnesium removing device 7 is connected with the liquid phase inlet of the heavy metal removing device 8, the liquid phase outlet of the heavy metal removing device 8 is connected with the liquid phase inlet of the flocculation and precipitation device 9, the liquid phase outlet of the flocculation and precipitation device 9 is connected with the liquid phase inlet of the multistage filtering device 10, and the liquid phase outlet of the multistage filtering device 10 is connected with the liquid phase inlet of the pH value adjusting device 12; a sludge outlet of the calcium and magnesium removal device 7, a sludge outlet of the heavy metal removal device 8, a sludge outlet of the flocculation precipitation device 9 and a sludge outlet of the multistage filtration device 10 are all connected with a sludge inlet of the desliming device 11; and a solid phase outlet of the desliming device 11 is connected with an inlet of the drying unit, a liquid phase outlet of the desliming device 11 is connected with a water washing liquid inlet of the calcium and magnesium removal device 7, and a liquid phase outlet of the pH value adjusting device 12 is connected with an inlet of the evaporation crystallization unit.
As a preferred embodiment of the invention, the evaporative crystallization unit comprises a multi-stage preheater 13, a falling film heat exchanger 14, a forced circulation heat exchanger 15, an evaporative crystallizer 16, a sodium chloride crystallization separator 17, a nanofiltration membrane treatment device 18 and a potassium chloride crystallization separator 19; the multi-stage preheater 13 is provided with an evaporation raw material liquid inlet, a preheating water inlet, a condensed water outlet and a liquid phase outlet; the falling film heat exchanger 14 is provided with a feed liquid inlet, a condensed water outlet and an evaporated liquid outlet; the forced circulation heat exchanger 15 is provided with a feed liquid inlet, a condensed water outlet and an evaporated liquid outlet; the evaporation crystallizer 16 is provided with an evaporation liquid inlet, a crystal slurry outlet and a strong brine outlet; the sodium chloride crystallization separator 17 is provided with a crystal slurry inlet, a sodium chloride crystallized salt outlet, a supernatant outlet and a mother liquor outlet; the nanofiltration membrane treatment device 18 is provided with a supernatant inlet, a clear liquid outlet and a concentrated liquid outlet; the potassium chloride crystal separator 19 is provided with a clear liquid inlet, a potassium chloride crystal salt outlet, a potassium chloride mother liquid outlet and a potassium chloride mother liquid outlet which does not crystallize;
wherein, an evaporation raw material liquid inlet of the multi-stage preheater 13 is connected with a liquid phase outlet of the pH value adjusting device 12 of the washing liquid purifying unit; a liquid phase outlet of the multi-stage preheater 13 is connected with a feed liquid inlet of the falling film heat exchanger 14, and an evaporation liquid outlet of the falling film heat exchanger 14 is connected with a feed liquid inlet of the forced circulation heat exchanger 15; an evaporation liquid outlet of the forced circulation heat exchanger 15 is connected with an evaporation liquid inlet of the evaporation crystallizer 16, a condensed water outlet of the falling film heat exchanger 14 and a condensed water outlet of the forced circulation heat exchanger 15 are connected with a preheated water inlet of the multi-stage preheater 13, a crystal slurry outlet of the evaporation crystallizer 16 is connected with a crystal slurry inlet of the sodium chloride crystallization separator 17, and a concentrated brine outlet of the evaporation crystallizer 16 is connected with a feed liquid inlet of the forced circulation heat exchanger 15; a sodium chloride mother liquor outlet of the sodium chloride crystallization separator 17 is connected with a feed liquid inlet of the forced circulation heat exchanger 15 through a mother liquor return pipeline, and a supernatant outlet of the sodium chloride crystallization separator 17 is connected with a supernatant inlet of the nanofiltration membrane treatment device 18; a clear liquid outlet of the nanofiltration membrane treatment device 18 is connected with a clear liquid inlet of the potassium chloride crystal separator 19; a potassium chloride mother liquor outlet of the potassium chloride crystallization separator 19 is connected with a feed liquor inlet of the forced circulation heat exchanger 15;
as a preferred embodiment of the invention, the concentrate outlet of the nanofiltration membrane treatment device 18 and the non-crystallized potassium chloride mother liquor outlet of the potassium chloride crystallization separator 19 are both connected with the inlet of the fly ash elution unit;
in a preferred embodiment of the invention, the nanofiltration membrane treatment device is provided with an insulating layer.
Various devices or apparatuses used in the invention are conventional devices in the technology of solid waste reprocessing or garbage fly ash reprocessing, and the devices can be purchased commercially and are all suitable for the invention; in addition, the related literature also discloses new devices with improved devices, and better technical effects can be achieved by using the new devices with improved devices, such as: fly ash pulping equipment (CN 204848668U, the name of the utility model is a fly ash washing device); a first-stage elution and separation device (CN 204848668U, the name of the utility model is a fly ash washing device), a second-stage elution and separation device (CN 204848668U, the name of the utility model is a fly ash washing device), and a third-stage elution and separation device (CN 204848668U, the name of the utility model is a fly ash washing device); a calcium and magnesium removing device (utility model name: a settling device for a fly ash washing liquid purifying system, CN 212369634U) and a multistage filtering device (CN 205627217U, utility model name: a quick-open type multi-medium filter).
The method and system of the present invention are further described below in conjunction with specific embodiments.
Example 1
Step (1): respectively weighing the waste incineration fly ash and pulping water, stirring and mixing, carrying out hydration reaction and pulping in a fly ash pulping device 3 according to the proportion of 1:3, and finally obtaining fly ash slurry.
Step (2): and (3) sequentially carrying out primary elution, secondary elution and tertiary elution on the fly ash slurry to obtain water washing liquid with the solid content of less than 1% and water washing fly ash with the water content of not more than 40%.
And (3): and (3) drying the washed fly ash in the step (2) by adopting steam or hot air as a drying medium (the set temperature of the drying medium is 230 ℃), and finally obtaining a fly ash finished product with the water content of less than 5%.
And (4): and (2) performing water quality purification treatment on the washing liquid obtained in the step (1), and sequentially performing calcium and magnesium removal, heavy metal removal, flocculation precipitation, multi-stage filtration, solid-liquid separation of slurry and pH value adjustment treatment to obtain an evaporation raw material liquid.
Step (4-1): conveying the water washing liquid generated by the first-stage elution to a calcium and magnesium removal device 7 added with sodium carbonate with a certain mass concentration for water softening treatment, and performing solid-liquid separation on the treated water washing liquid to obtain clear liquid and wet mud;
step (4-2): the clear liquid in the step (4-1) enters a heavy metal removal device 8 added with a heavy metal trapping agent (sodium sulfide, sodium thiosulfate and a special medicament) with a certain mass concentration, the heavy metal content in the water is reduced, and the water washing liquid after heavy metal removal is subjected to solid-liquid separation to obtain clear liquid and wet mud;
step (4-3): the clear liquid in the step (4-2) enters a flocculation precipitation device 9 added with a flocculation precipitation medicament with certain mass concentration to obtain the clear liquid and wet mud;
step (4-4): and (4) enabling the supernatant obtained in the step (4-3) to enter a multistage filtering device 10(10 mu m, 5 mu m and 1 mu m) to obtain filtrate and filter residues (namely wet mud).
Step (4-5): the filtrate obtained in the step (4-4) enters a pH value adjusting device 12, and acidic reagents (more than one of hydrochloric acid, sulfuric acid and the like) with certain mass concentration need to be added into the pH value adjusting device 12, so as to finally obtain an evaporation raw material liquid;
step (4-6): and (4) the wet sludge in the steps (4-1) to (4-4) enters a desliming device 11 for treatment, the generated sludge enters a drying unit along with washed ash for drying treatment, and the generated liquid phase enters a calcium and magnesium removal device 7 for retreatment.
And (5): and (4) sequentially carrying out preheating, heat exchange, evaporation, crystallization separation and nanofiltration treatment on the evaporation raw material liquid obtained in the step (4), and finally obtaining sodium chloride and potassium chloride products.
Step (5-1): preheating raw material liquid in a multi-stage preheater 13 and raising the temperature to 90-100 ℃ for steaming;
step (5-2): the preheated feed liquid enters a falling film preheater 14 for cyclic heating and evaporation, the temperature in the falling film heat exchanger 14 is controlled to be 90-100 ℃, and the next operation is carried out when the solid-to-liquid ratio in the feed liquid reaches 20-25%;
step (5-3): the feed liquid treated in the step (5-2) enters a forced circulation heat exchanger 15 for evaporation and concentration treatment, the temperature of the heat exchanger program is set to be 110 ℃, and the next operation is carried out when the solid-liquid ratio of the feed liquid is more than or equal to 30%;
step (5-4): the concentrated feed liquid enters an evaporation crystallizer 16, and after crystallization and layering in the evaporation crystallizer 16, crystal slurry with the salt content of 30 wt% -60 wt% and concentrated brine are obtained. Conveying the concentrated brine to a forced circulation heat exchanger 15 for continuous evaporation and concentration treatment; and (3) allowing the crystal slurry to enter a sodium chloride crystallization separator 17, and separating the crystallized salt from the feed liquid to obtain sodium chloride crystallized salt with the water content of not more than 6 wt%, supernatant and sodium chloride mother liquor.
Step (5-5): and (5) when the supernatant in the step (5-4) reaches a potassium chloride saturated solution, sending the supernatant into a nanofiltration membrane treatment device 18, and treating to obtain a clear liquid and a concentrated liquid. The concentrated solution returns to the fly ash elution unit, and the clear solution enters a potassium chloride crystallization separator 19.
Step (5-6): cooling the clear liquid in a potassium chloride crystal separator 19, separating the crystallized salt from the feed liquid when the temperature is reduced to 10-50 ℃ and crystals are separated out to obtain potassium chloride crystallized salt with the water content not more than 6 wt%, potassium chloride mother liquid and non-crystallized potassium chloride mother liquid; discharging the potassium chloride mother liquor which is not crystallized to a fly ash elution unit.
Step (5-7): and (4) conveying the sodium chloride mother liquor in the step (5-4) and the potassium chloride mother liquor in the step (5-6) to a forced circulation heat exchanger 15 for continuous evaporation and concentration treatment.
Furthermore, condensed water (the temperature of the condensed water is 80-100 ℃) generated in the falling film heat exchange and forced circulation heat exchange processes is used for preheating water of the multistage preheater;
furthermore, condensed water generated in the multi-stage preheating process is sent to the fly ash elution unit to be used as water for pulping.
Claims (10)
1. A treatment method for water washing dechlorination of waste incineration fly ash and evaporation mass-separation crystallization of water washing liquid is characterized by comprising the following steps: (1) stirring the waste incineration fly ash and pulping water to prepare fly ash slurry; (2) performing multi-stage elution on the fly ash slurry by using water to obtain water-washed fly ash and water-washed liquid; (3) purifying the water washing liquid to obtain clear liquid and precipitated slurry; adjusting the pH value of the clear liquid to obtain an evaporation raw material liquid; (4) sequentially carrying out preheating treatment, falling film heat exchange treatment, forced circulation heat exchange treatment, evaporation crystallization treatment, sodium chloride crystallization separation treatment, nanofiltration membrane treatment and potassium chloride crystallization separation treatment on the evaporation raw material liquid to obtain potassium chloride and sodium chloride products; (5) carrying out desliming treatment on the precipitated slurry obtained in the step (3) to obtain sludge and clear liquid; and (3) drying the sludge and the water-washed fly ash generated in the step (2) to obtain a fly ash finished product.
2. The treatment method according to claim 1, wherein in the step (1), the mass ratio of the waste incineration fly ash to the pulping water is preferably 1:2-1:4, and most preferably 1: 3;
the multi-stage elution in the step (2) is three-stage elution; preferably, the tertiary elution comprises: putting the fly ash slurry prepared in the step (1) into a primary elution separation device for primary elution to obtain primary washing fly ash and primary washing liquid; mixing the first-stage washing fly ash with pulping water to obtain first-stage fly ash slurry, and allowing the first-stage fly ash slurry to enter a second-stage elution separation device for second-stage elution to obtain second-stage washing fly ash and second-stage washing liquid; mixing the second-stage water-washing fly ash with pulping water to obtain second-stage fly ash slurry, and performing third-stage elution on the second-stage fly ash slurry in a third-stage elution separation device to obtain third-stage water-washing fly ash and third-stage water-washing liquid; drying the three-stage washing fly ash to obtain a fly ash finished product;
more preferably, the secondary water washing liquid is used as the pulping water in the step (1), and the tertiary water washing liquid is used as the pulping water in the second-stage elution; circulating water and makeup water are used as pulping water for the third-stage elution, and clear water is used as the pulping water for the third-stage elution during initial work.
3. The treatment method according to claim 1, wherein the first-stage water washing liquid in the step (2) is adopted in the step (3) for purification treatment to obtain clear liquid and precipitated slurry, wherein the purification treatment sequentially comprises calcium and magnesium ion removal, heavy metal removal, flocculation precipitation treatment and multi-stage filtration treatment to finally obtain the clear liquid and the precipitated slurry;
preferably, the calcium and magnesium ion removal is to add sodium carbonate into a calcium and magnesium ion removal device to perform calcium and magnesium ion removal treatment; the heavy metal removal treatment is to add a heavy metal catching agent into a heavy metal removal device to carry out heavy metal removal treatment; the flocculation precipitation treatment is to add a flocculation precipitation medicament for flocculation precipitation reaction; the multistage filtration treatment is to sequentially filter by filtration membranes with the filtration pore diameters of 10 microns, 5 microns and 1 micron; the pH value is adjusted to 6-8 by using an acidic solution.
4. The process according to claim 1, wherein the preheating treatment in the step (4) is preheating of the evaporation raw material liquid at a temperature of 80 ℃ to 110 ℃; the falling film heat exchange treatment comprises the steps of feeding preheated feed liquid into a falling film heat exchanger for heating evaporation, wherein the temperature in the falling film heat exchanger is controlled to be 80-100 ℃, the feed liquid is circularly heated and evaporated in the falling film heat exchanger, the feed liquid enters a forced circulation heat exchanger for forced circulation heat exchange treatment when the solid-to-liquid ratio in the feed liquid reaches 20-25%, the temperature of the forced circulation heat exchanger is controlled to be 90-120 ℃, the feed liquid is evaporated and concentrated, the feed liquid obtained after evaporation and concentration enters an evaporation crystallizer, and crystal slurry and concentrated brine are obtained after crystallization and layering in the evaporation crystallizer; conveying the strong brine to a forced circulation heat exchanger for continuous evaporation and concentration, introducing the crystal slurry into a sodium chloride crystallization separator for crystallization to obtain crystallized salt and feed liquid, and separating the crystallized salt and the feed liquid to obtain sodium chloride crystallized salt, supernatant and sodium chloride mother liquor; when the supernatant reaches a potassium chloride saturated solution, sending the supernatant into a nanofiltration membrane treatment device, and treating to obtain a clear liquid and a concentrated liquid; carrying out multi-stage elution on the concentrated solution to obtain washing fly ash and washing liquid; the clear liquid enters a potassium chloride crystallization separator to be cooled and crystallized to obtain crystallized salt and feed liquid, and the crystallized salt and the feed liquid are separated to obtain potassium chloride crystallized salt, potassium chloride mother liquid and non-crystallized potassium chloride mother liquid; carrying out multi-stage elution treatment on the potassium chloride mother liquor which is not crystallized to obtain washing fly ash and washing liquor; and conveying the sodium chloride mother liquor and the potassium chloride mother liquor to a forced circulation heat exchanger for evaporation and concentration treatment.
5. The process according to claim 4, wherein the condensed water produced in the falling film heat exchange treatment and forced circulation heat exchange treatment is used as preheating water in the multistage preheating process; and the condensed water generated in the multi-stage preheating process is used as water for pulping when the fly ash is eluted.
6. A system for implementing the treatment method as claimed in any one of claims 1 to 5, wherein the system comprises a fly ash pulping unit, a fly ash elution unit, a water washing liquid purification unit, an evaporative crystallization unit and a drying unit; the fly ash pulp making unit is provided with a fly ash pulp outlet, and the fly ash eluting unit is provided with a fly ash pulp inlet, a solid-phase product outlet, a liquid-phase product outlet and a pulp making water inlet; the washing liquid purification unit is provided with a liquid phase inlet, a liquid phase outlet and a solid phase outlet; the evaporative crystallization unit is provided with an evaporative raw material liquid inlet, a non-crystallization mother liquid outlet and a condensed water outlet;
the device comprises a fly ash pulping unit, a fly ash washing unit, a drying unit, a water washing liquid purifying unit, a fly ash pulp outlet of the fly ash pulping unit, a fly ash pulp inlet of the fly ash washing unit, a solid-phase product outlet of the fly ash washing unit, a liquid-phase inlet of the water washing liquid purifying unit, a liquid-phase outlet of the water washing liquid purifying unit, an evaporation raw material liquid inlet of the evaporation crystallization unit, a solid-phase outlet of the water washing liquid purifying unit, an inlet of the drying unit, an outlet of non-crystallization mother liquid of the evaporation crystallization unit, a liquid-phase inlet of the water washing liquid purifying unit and a condensed water outlet of the evaporation crystallization unit, wherein the fly ash pulp inlet of the fly ash washing unit is.
7. A system according to claim 6, characterized in that the fly ash pulping unit comprises a fly ash metering device (1), a pulping water metering device (2) and a pulping apparatus (3); the fly ash metering device (1) is provided with a fly ash inlet and a fly ash outlet, the pulping water metering device (2) is provided with a pulping water inlet and a pulping water outlet, the pulping equipment (3) is provided with a fly ash feeding hole, a pulping water inlet and a fly ash slurry outlet, wherein the fly ash outlet of the fly ash metering device (1) is connected with the fly ash feeding hole of the pulping equipment (3), and the pulping water outlet of the pulping water metering device (2) is connected with the pulping water inlet of the pulping equipment (3).
8. A system according to claim 6, characterized in that the fly ash elution unit comprises a primary elution separation device (4), a secondary elution separation device (5) and a tertiary elution separation device (6); the first-stage elution separation device (4) is provided with a fly ash slurry inlet, a water washing liquid outlet and a solid phase outlet; the secondary elution separation device (5) is provided with a slurry inlet, a solid phase outlet and a liquid phase inlet; the third-stage elution separation device (6) is provided with a slurry inlet, a solid-phase outlet and a liquid-phase outlet; wherein, the wash liquor export of one-level elution separator (4) with the wash liquor entry of wash liquor purification unit link to each other, the solid phase export of one-level elution separator (4) with the thick liquid entry of second grade elution separator (5) link to each other, the liquid phase export of second grade elution separator (5) with the slurrying water import of slurrying water metering device (2) of slurrying unit link to each other, the solid phase export of second grade elution separator (5) with the thick liquid entry of third grade elution separator (6) link to each other, the liquid phase export of third grade elution separator (6) with the liquid phase entry of second grade elution separator (5) link to each other, the solid phase export of third grade elution separator (6) the entry of drying unit links to each other.
9. The system according to claim 6, characterized in that the washing liquid purification unit comprises a calcium and magnesium removal device (7), a heavy metal removal device (8), a flocculation precipitation device (9), a multi-stage filtration device (10), a desliming device (11) and a pH value adjusting device (12); the calcium and magnesium removing device (7) is provided with a washing liquid inlet, a liquid phase outlet and a sludge outlet; the heavy metal removal device (8) is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the flocculation precipitation device (9) is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the multistage filtering device (10) is provided with a liquid phase inlet, a liquid phase outlet and a sludge outlet; the desliming device (11) is provided with a sludge inlet, a solid phase outlet and a liquid phase outlet; the pH value adjusting device (12) is provided with a liquid phase inlet and a liquid phase outlet; wherein a water washing liquid inlet of the calcium and magnesium removing device (7) is connected with a liquid phase outlet of a first-stage elution separation device (4) of the fly ash elution unit, a liquid phase outlet of the calcium and magnesium removing device (7) is connected with a liquid phase inlet of the heavy metal removing device (8), a liquid phase outlet of the heavy metal removing device (8) is connected with a liquid phase inlet of a flocculation precipitation device (9), a liquid phase outlet of the flocculation precipitation device (9) is connected with a liquid phase inlet of the multistage filtering device (10), and a liquid phase outlet of the multistage filtering device (10) is connected with a liquid phase inlet of the pH value adjusting device (12); a sludge outlet of the calcium and magnesium removal device (7), a sludge outlet of the heavy metal removal device (8), a sludge outlet of the flocculation precipitation device (9) and a sludge outlet of the multistage filtering device (10) are all connected with a sludge inlet of the desliming device (11); the solid phase outlet of the desliming device (11) is connected with the inlet of the drying unit, the liquid phase outlet of the desliming device (11) is connected with the water washing liquid inlet of the calcium and magnesium removing device (7), and the liquid phase outlet of the pH value adjusting device (12) is connected with the inlet of the evaporation crystallization unit.
10. The system according to claim 6, wherein the evaporative crystallization unit comprises a multi-stage preheater (13), a falling film heat exchanger (14), a forced circulation heat exchanger (15), an evaporative crystallizer (16), a sodium chloride crystallization separator (17), a nanofiltration membrane treatment device (18), a potassium chloride crystallization separator (19); the multi-stage preheater (13) is provided with an evaporation raw material liquid inlet, a preheating water inlet, a condensed water outlet and a liquid phase outlet; the falling film heat exchanger (14) is provided with a feed liquid inlet, a condensed water outlet and an evaporated liquid outlet; the forced circulation heat exchanger (15) is provided with a feed liquid inlet, a condensed water outlet and an evaporated liquid outlet; the evaporation crystallizer (16) is provided with an evaporation liquid inlet, a crystal slurry outlet and a concentrated salt solution outlet; the sodium chloride crystallization separator (17) is provided with a crystal slurry inlet, a sodium chloride crystallized salt outlet, a supernatant outlet and a mother liquor outlet; the nanofiltration membrane treatment device (18) is provided with a supernatant inlet, a clear liquid outlet and a concentrated liquid outlet; the potassium chloride crystallization separator (19) is provided with a clear liquid inlet, a potassium chloride crystallized salt outlet, a potassium chloride mother liquid outlet and a potassium chloride mother liquid outlet which does not crystallize;
wherein an evaporation raw material liquid inlet of the multi-stage preheater (13) is connected with a liquid phase outlet of a pH value adjusting device (12) of the washing liquid purifying unit; a liquid phase outlet of the multi-stage preheater (13) is connected with a feed liquid inlet of the falling film heat exchanger (14), and an evaporation liquid outlet of the falling film heat exchanger (14) is connected with a feed liquid inlet of the forced circulation heat exchanger (15); an evaporation liquid outlet of the forced circulation heat exchanger (15) is connected with an evaporation liquid inlet of the evaporation crystallizer (16), a condensed water outlet of the falling film heat exchanger (14) and a condensed water outlet of the forced circulation heat exchanger (15) are connected with a preheated water inlet of the multi-stage preheater (13), a crystal slurry outlet of the evaporation crystallizer (16) is connected with a crystal slurry inlet of the sodium chloride crystallization separator (17), and a concentrated salt solution outlet of the evaporation crystallizer (16) is connected with a feed liquid inlet of the forced circulation heat exchanger (15); a sodium chloride mother liquor outlet of the sodium chloride crystallization separator (17) is connected with a feed liquid inlet of the forced circulation heat exchanger (15) through a mother liquor return pipeline, and a supernatant outlet of the sodium chloride crystallization separator (17) is connected with a supernatant inlet of the nanofiltration membrane treatment device (18); a clear liquid outlet of the nanofiltration membrane treatment device (18) is connected with a clear liquid inlet of the potassium chloride crystal separator (19); a potassium chloride mother liquor outlet of the potassium chloride crystallization separator (19) is connected with a feed liquor inlet of the forced circulation heat exchanger (15);
a concentrated solution outlet of the nanofiltration membrane treatment device (18) and a non-crystallized potassium chloride mother solution outlet of the potassium chloride crystallization separator (19) are connected with an inlet of a fly ash elution unit;
the nanofiltration membrane treatment device is provided with a heat insulation layer.
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Denomination of invention: The treatment method and system for chlorine removal from waste incineration fly ash by water washing and evaporative crystallization of water washing solution Granted publication date: 20230919 Pledgee: Bank of Beijing Co.,Ltd. Dongdaqiao Branch Pledgor: BJ ZKGR TECHNOLOGY CO.,LTD. Registration number: Y2024980010348 |