CN114226421A - Treatment method of semidry desulfurization ash - Google Patents
Treatment method of semidry desulfurization ash Download PDFInfo
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- CN114226421A CN114226421A CN202111607015.0A CN202111607015A CN114226421A CN 114226421 A CN114226421 A CN 114226421A CN 202111607015 A CN202111607015 A CN 202111607015A CN 114226421 A CN114226421 A CN 114226421A
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- fly ash
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- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 11
- 230000023556 desulfurization Effects 0.000 title abstract description 11
- 239000010881 fly ash Substances 0.000 claims abstract description 65
- 239000002131 composite material Substances 0.000 claims abstract description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002351 wastewater Substances 0.000 claims abstract description 31
- 239000012265 solid product Substances 0.000 claims abstract description 25
- 239000002956 ash Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 238000009210 therapy by ultrasound Methods 0.000 claims description 51
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 50
- 239000003795 chemical substances by application Substances 0.000 claims description 47
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 34
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 30
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 30
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 25
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 23
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 23
- 239000010902 straw Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000005086 pumping Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 5
- 239000002920 hazardous waste Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 11
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract description 8
- 239000000920 calcium hydroxide Substances 0.000 abstract description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract description 8
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 abstract description 8
- 235000010261 calcium sulphite Nutrition 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 4
- 239000011787 zinc oxide Substances 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 description 11
- 235000011116 calcium hydroxide Nutrition 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- -1 chlorine ions Chemical class 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for treating semi-dry desulfurized fly ash, and particularly relates to the technical field of desulfurized fly ash. According to the invention, the desulfurized fly ash is added into the oxidation tank, hydrogen peroxide is added, and oxygen is introduced into water for oxidation treatment, so that calcium sulfite and calcium hydroxide can be effectively oxidized and converted into calcium sulfate and calcium carbonate, the desulfurized fly ash of solid waste can be effectively and rapidly converted into a byproduct which can bring benefits, the content of chloride ions in waste water can be effectively reduced, the content of residual calcium sulfite and calcium hydroxide in solid products is extremely low, and the conversion rate is high; the composite material of the nano manganese dioxide, the nano aluminum oxide, the nano silver particles, the nano zinc oxide, the graphene oxide and the reduced graphene oxide is compounded into the activated carbon, so that the removal effect of chloride ions in wastewater can be effectively enhanced, the purification of wastewater generated by desulfurization ash treatment can be further enhanced, and the quality of the wastewater is further improved.
Description
Technical Field
The invention relates to the technical field of desulfurized fly ash, in particular to a method for treating desulfurized fly ash by a semidry method.
Background
The main component of the industrial waste desulfurized fly ash is gypsum which is very cheap, the cost for recycling and fully utilizing the gypsum is very high, and the industrial waste desulfurized fly ash can be directly discarded. The semi-dry desulfurization processing technology of the desulfurized fly ash is widely applied to flue gas desulfurization engineering projects of sintering, pelletizing and coal-fired power plants of steel enterprises in China at present due to the advantages of short production process, small occupied area, less project investment, simple control, low water consumption, no white smoke and rain and the like. Most of the products in wet calcium-based desulfurization are calcium sulfate CaSO4Gypsum, commonly known as cement, is a raw material for cement production, can be used in the building industry, is a byproduct, and can bring benefits to users in the treatment process. Desulfurized ash the semidry desulfurized ash is a byproduct formed by the semidry flue gas desulfurization processing technology, and comprises the following main components: free calcium oxide, calcium sulfite, calcium carbonate, calcium sulfate, calcium hydroxide and other chemical substances. The semi-dry desulphurization is widely applied to tail gas treatment of electric power, steel and cement, and the desulfurizer is calcium oxide CaO or hydrated lime Ca (OH)2。
CaSO in desulfurized fly ash due to process limitations4Low content of calcium sulfite CaSO3Relatively high in content and containing a part of unreacted Ca (OH)2It cannot be used in cement technology or building industry, belongs to solid waste, and needs to be disposed at high cost.
Disclosure of Invention
In order to overcome the above-mentioned drawbacks of the prior art, embodiments of the present invention provide a method for treating semi-dry desulfurized fly ash.
A treatment method of semidry desulfurization ash comprises the following specific treatment steps:
the method comprises the following steps: adding metered desulfurized ash into an oxidation tank, adding water, stirring for 5-9 minutes, adding hydrogen peroxide, continuing stirring for 30-40 minutes, and introducing air into the bottom of the inner side of the oxidation tank during stirring to obtain slurry;
step two: pumping the slurry into a dehydrator by a slurry pump for dehydration to obtain a solid product and wastewater;
step three: adding a composite treating agent into the wastewater, continuously stirring for 30-40 minutes, simultaneously performing ultrasonic treatment for 5-10 minutes, and pumping the wastewater into a separation device through a wastewater pump to obtain separated water liquid and waste residues;
step four: the separated water liquid can be reused, and the separated waste residue is treated as hazardous waste.
Further, in the first step, the stirring speed is 130-140 RPM, the air introduction amount is 50-60 ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 20-30; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 10-12; in the third step, the addition amount of the composite treating agent is as follows: 105-125 mg/L;
further, in the first step, the stirring speed is 130RPM, the air introduction amount is 50ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 20; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 10; in the third step, the addition amount of the composite treating agent is as follows: 105 mg/L;
further, in the first step, the stirring speed is 135RPM, the air introduction amount is 55ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 25; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 11; in the third step, the addition amount of the composite treating agent is as follows: 115 mg/L;
the composite treating agent in the first step comprises the following components in percentage by weight: 1.9-2.3% of graphene oxide, 2.8-3.2% of potassium manganate, 2.8-3.2% of aluminum nitrate, 2.9-3.5% of silver nitrate, 3.1-3.5% of zinc nitrate, 2.3-2.5% of sodium hydroxide, 16.6-17.2% of hydrazine hydrate and the balance of straw;
the preparation process of the composite treating agent comprises the following specific preparation steps:
s1: weighing graphene oxide, potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, straws, sodium hydroxide and hydrazine hydrate according to the weight percentage;
s2: firstly stirring and dissolving potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, sodium hydroxide and two-thirds by weight of hydrazine hydrate in deionized water to obtain a mixed solution A, then dissolving crushed straws in the mixed solution A, and stirring for 1-2 hours to obtain a mixed material B;
s3: adding the mixture B into a reaction kettle, reacting at 180-230 ℃ for 12-15 h, simultaneously carrying out ultrasonic treatment to obtain a solid product, washing the solid product with deionized water at room temperature, and drying at 108-112 ℃;
s4: heating the solid product dried in the step S3 to 700-780 ℃ under activated gas, keeping the temperature for 2.5-3.5 h, and cooling to obtain a mixture C;
s5: and (4) uniformly mixing the mixture C with the graphene oxide and the residual hydrazine hydrate in the step S1, adding the mixture C into deionized water, carrying out ultrasonic treatment for 10-20 minutes, and dehydrating and drying to obtain the composite treating agent.
Further, the composite treating agent comprises the following components in percentage by weight: 1.9% of graphene oxide, 2.8% of potassium manganate, 2.8% of aluminum nitrate, 2.9% of silver nitrate, 3.1% of zinc nitrate, 2.3% of sodium hydroxide, 16.6% of hydrazine hydrate and 67.6% of straws.
Further, the composite treating agent comprises the following components in percentage by weight: 2.3% of graphene oxide, 3.2% of potassium manganate, 3.2% of aluminum nitrate, 3.5% of silver nitrate, 3.5% of zinc nitrate, 2.5% of sodium hydroxide, 17.2% of hydrazine hydrate and 64.6% of straws.
Further, the composite treating agent comprises the following components in percentage by weight: 2.1% of graphene oxide, 3.0% of potassium manganate, 3.0% of aluminum nitrate, 3.2% of silver nitrate, 3.3% of zinc nitrate, 2.4% of sodium hydroxide, 16.9% of hydrazine hydrate and 66.1% of straws.
Further, in the step S3 and the step S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, the ultrasonic treatment is performed once every 1 to 2 hours, each time of ultrasonic treatment is 20 to 30 minutes, the ultrasonic frequency is 22 to 26KHz, and the ultrasonic power is 1000 to 1200W.
Further, in step S3 and step S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, wherein ultrasonic treatment is performed every 1.5 hours for 25 minutes, the ultrasonic frequency is 24KHz, and the ultrasonic power is 1100W.
The invention has the technical effects and advantages that:
1. by adopting the method for treating the semi-dry desulfurized fly ash, the desulfurized fly ash is added into the oxidation tank in the first step, hydrogen peroxide is added, and oxygen is introduced into water for oxidation treatment, so that calcium sulfite and calcium hydroxide can be effectively oxidized and converted into calcium sulfate and calcium carbonate, and the desulfurized fly ash of solid waste can be effectively and quickly converted into a byproduct which can bring benefits; the content of residual calcium sulfite and calcium hydroxide in the solid product is extremely low, and the conversion rate is high; the composite treating agent can effectively improve the purification treatment effect on the wastewater; dehydrating the slurry in the second step; treating and separating the wastewater in the third step; in the fourth step, the water liquid is recycled, and the waste residue is treated with hazardous waste;
2. in the using process of the composite treating agent, silver nitrate is reduced into simple substance silver under the action of hydrazine hydrate serving as a reducing agent in the preparation process of graphene oxide in the composite treating agent, nano silver particles are formed, the graphene oxide is partially reduced to form a composite material of the graphene oxide and the reduced graphene oxide, and the nano manganese dioxide, the nano aluminum sesquioxide, the nano silver particles and the composite material of the nano zinc oxide, the graphene oxide and the reduced graphene oxide are compounded into the activated carbon, so that the removal effect of chlorine ions in the wastewater can be effectively enhanced, the purification of the wastewater generated by desulfurization ash treatment can be further enhanced, the quality of the wastewater is further improved, the difficulty of subsequent wastewater treatment is reduced, the wastewater treatment is more convenient and rapid, and the wastewater treatment effect is better.
Detailed Description
The following will clearly and completely describe the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the invention provides a method for treating semi-dry desulfurized fly ash, which comprises the following specific treatment steps:
the method comprises the following steps: adding metered desulfurized ash into an oxidation tank, adding water, stirring for 5 minutes, adding hydrogen peroxide, continuously stirring for 30 minutes, and introducing air into the bottom of the inner side of the oxidation tank during stirring to obtain slurry;
step two: pumping the slurry into a dehydrator by a slurry pump for dehydration to obtain a solid product and wastewater;
step three: adding the composite treating agent into the wastewater, continuously stirring for 30 minutes, simultaneously performing ultrasonic treatment for 5 minutes, and pumping into a separation device through a wastewater pump to obtain separated water liquid and waste residue;
step four: the separated water liquid can be reused, and the separated waste residue is treated with hazardous waste;
in the first step, the stirring speed is 130RPM, the air input is 50ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 20; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 10; in the third step, the addition amount of the composite treating agent is as follows: 105 mg/L;
the preparation process of the composite treating agent comprises the following specific preparation steps:
the composite treating agent in the first step comprises the following components in percentage by weight: 1.9% of graphene oxide, 2.8% of potassium manganate, 2.8% of aluminum nitrate, 2.9% of silver nitrate, 3.1% of zinc nitrate, 2.3% of sodium hydroxide, 16.6% of hydrazine hydrate and 67.6% of straws;
the preparation process of the composite treating agent comprises the following specific preparation steps:
s1: weighing graphene oxide, potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, straws, sodium hydroxide and hydrazine hydrate according to the weight percentage;
s2: firstly stirring and dissolving potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, sodium hydroxide and two-thirds by weight of hydrazine hydrate in deionized water to obtain a mixed solution A, then dissolving crushed straws in the mixed solution A, and stirring for 1 hour to obtain a mixed material B;
s3: adding the mixture B into a reaction kettle, reacting for 12 hours at 180 ℃, simultaneously carrying out ultrasonic treatment to obtain a solid product, washing the solid product with deionized water at room temperature, and drying at 108 ℃;
s4: heating the solid product dried in the step S3 to 700 ℃ under activated gas, keeping the temperature for 2.5 hours, and cooling to obtain a mixture C;
s5: and (4) uniformly mixing the mixture C with the graphene oxide and the residual hydrazine hydrate in the step S1, adding the mixture C into deionized water, carrying out ultrasonic treatment for 10 minutes, and dehydrating and drying to obtain the composite treating agent.
In steps S3 and S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, wherein ultrasonic treatment is carried out once every 1 hour, each ultrasonic treatment is carried out for 20 minutes, the ultrasonic frequency is 22KHz, and the ultrasonic power is 1000W.
Example 2:
different from the embodiment 1, the composite treating agent comprises the following components in percentage by weight: 2.3% of graphene oxide, 3.2% of potassium manganate, 3.2% of aluminum nitrate, 3.5% of silver nitrate, 3.5% of zinc nitrate, 2.5% of sodium hydroxide, 17.2% of hydrazine hydrate and 64.6% of straws.
Example 3:
different from the embodiments 1-2, the composite treating agent comprises the following components in percentage by weight: 2.1% of graphene oxide, 3.0% of potassium manganate, 3.0% of aluminum nitrate, 3.2% of silver nitrate, 3.3% of zinc nitrate, 2.4% of sodium hydroxide, 16.9% of hydrazine hydrate and 66.1% of straws.
Taking the method for treating the semi-dry desulfurized fly ash in the first embodiment 1-3 and the method for treating the semi-dry desulfurized fly ash in the first control group, the method for treating the semi-dry desulfurized fly ash in the second control group, the method for treating the semi-dry desulfurized fly ash in the third control group, the method for treating the semi-dry desulfurized fly ash in the fourth control group, the method for treating the semi-dry desulfurized fly ash in the fifth control group and the method for treating the semi-dry desulfurized fly ash in the sixth control group, respectively, the method for treating the semi-dry desulfurized fly ash in the first control group and the three-phase ratio composite treating agent in the first embodiment do not contain graphene oxide; the treatment method of the semi-dry desulfurized fly ash of the control group II does not contain potassium manganate in the composite treating agent compared with the three phases of the embodiment; the semi-dry desulfurized ash of the third control group has no aluminum nitrate in the composite treating agent compared with the three phases of the embodiment; the semi-dry desulfurized ash of the control group IV has no silver nitrate in the composite treating agent compared with the three phases of the embodiment; the treatment method of the semi-dry desulfurized fly ash of the control group five does not contain zinc nitrate in the composite treatment agent compared with the three phases of the embodiment; the semi-dry desulfurized ash treatment method of the control group VI does not have straws in the composite treatment agent compared with the three phases of the embodiment; the solid product and the water liquid after wastewater treatment processed in the three examples, and the solid product and the water liquid after wastewater treatment processed by the treatment method of the semi-dry desulfurization ash of the six control groups were tested in nine groups, and the test results are shown in table one:
table one:
as can be seen from Table I, when the composite treating agent comprises the following components in percentage by weight: 2.1 percent of graphene oxide, 3.0 percent of potassium manganate, 3.0 percent of aluminum nitrate, 3.2 percent of silver nitrate, 3.3 percent of zinc nitrate, 2.4 percent of sodium hydroxide, 16.9 percent of hydrazine hydrate and 66.1 percent of straws, the content of chloride ions in the wastewater can be effectively reduced, and CaSO in solid products3And Ca (OH)2The weight percentage in the solid product is the lowest, so example 3 is the preferred embodiment of the present invention; in the first step, the desulfurized fly ash is added into an oxidation tank, hydrogen peroxide is added,oxygen is introduced into the water for oxidation treatment, so that calcium sulfite and calcium hydroxide can be effectively oxidized and converted into calcium sulfate and calcium carbonate, and the desulfurized ash of the solid waste can be effectively and quickly converted into a byproduct which can bring benefits; the content of residual calcium sulfite and calcium hydroxide in the solid product is extremely low, and the conversion rate is high; in the third step, the wastewater is treated and separated, and the graphene oxide in the composite treating agent is partially reduced under the action of hydrazine hydrate as a reducing agent in the preparation process of the graphene oxide to form a composite material of the graphene oxide and the reduced graphene oxide, so that the purification treatment of water quality can be effectively enhanced, the quality of the wastewater is improved, the difficulty of subsequent wastewater treatment is reduced, the wastewater treatment is more convenient, and the wastewater treatment effect is better; the potassium manganate, the aluminum nitrate, the silver nitrate, the zinc nitrate, the straw, the sodium hydroxide and the hydrazine hydrate are subjected to a common soaking reaction treatment, the hydrazine hydrate is used for reducing silver ions in the silver nitrate to form nano silver particles, and then the nano silver particles are calcined to effectively prepare the active carbon composite material loaded with the nano manganese dioxide, the nano aluminum oxide, the nano silver particles and the nano zinc oxide; the nano manganese dioxide can effectively promote the degradation of phenol organic pollutants in the wastewater; the nano aluminum oxide can effectively improve the adsorption treatment effect on the wastewater; the composite material of the nano manganese dioxide, the nano aluminum sesquioxide, the nano silver particles and the nano zinc oxide, the graphene oxide and the reduced graphene oxide is compounded into the activated carbon, so that the removal effect of chloride ions in wastewater can be effectively enhanced, the purification of wastewater generated by desulfurization ash treatment can be further enhanced, the quality of the wastewater is further improved, the difficulty of subsequent wastewater treatment is reduced, the wastewater treatment is more convenient and rapid, and the wastewater treatment effect is better; in the fourth step, the water liquid is reused, and the waste residue is treated by dangerous waste.
Example 4:
the invention provides a method for treating semi-dry desulfurized fly ash, which comprises the following specific treatment steps:
the method comprises the following steps: adding metered desulfurized ash into an oxidation tank, adding water, stirring for 7 minutes, adding hydrogen peroxide, continuously stirring for 35 minutes, and introducing air into the bottom of the inner side of the oxidation tank during stirring to obtain slurry;
step two: pumping the slurry into a dehydrator by a slurry pump for dehydration to obtain a solid product and wastewater;
step three: adding the composite treating agent into the wastewater, continuously stirring for 35 minutes, simultaneously performing ultrasonic treatment for 8 minutes, and pumping into a separation device through a wastewater pump to obtain separated water liquid and waste residue;
step four: the separated water liquid can be reused, and the separated waste residue is treated with hazardous waste;
in the first step, the stirring speed is 130RPM, the air input is 50ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 20; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 10; in the third step, the addition amount of the composite treating agent is as follows: 105 mg/L;
the preparation process of the composite treating agent comprises the following specific preparation steps:
the composite treating agent in the first step comprises the following components in percentage by weight: 2.1% of graphene oxide, 3.0% of potassium manganate, 3.0% of aluminum nitrate, 3.2% of silver nitrate, 3.3% of zinc nitrate, 2.4% of sodium hydroxide, 16.9% of hydrazine hydrate and 66.1% of straws;
the preparation process of the composite treating agent comprises the following specific preparation steps:
s1: weighing graphene oxide, potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, straws, sodium hydroxide and hydrazine hydrate according to the weight percentage;
s2: firstly, stirring and dissolving potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, sodium hydroxide and two-thirds by weight of hydrazine hydrate in deionized water to obtain a mixed solution A, then dissolving crushed straws in the mixed solution A, and stirring for 1.5 hours to obtain a mixed material B;
s3: adding the mixture B into a reaction kettle, reacting for 12 hours at 180-230 ℃, simultaneously carrying out ultrasonic treatment to obtain a solid product, washing the solid product with deionized water at room temperature, and drying at 110 ℃;
s4: heating the solid product dried in the step S3 to 740 ℃ under activated gas, keeping the temperature for 3.0h, and cooling to obtain a mixture C;
s5: and (4) uniformly mixing the mixture C with the graphene oxide and the residual hydrazine hydrate in the step S1, adding the mixture C into deionized water, carrying out ultrasonic treatment for 15 minutes, and dehydrating and drying to obtain the composite treating agent.
In steps S3 and S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, wherein ultrasonic treatment is carried out once every 1 hour, each ultrasonic treatment is carried out for 20 minutes, the ultrasonic frequency is 22KHz, and the ultrasonic power is 1000W.
Example 5:
different from the example 4, in the step one, the stirring speed is 140RPM, the air input is 60ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 30; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 12; in the third step, the addition amount of the composite treating agent is as follows: 125 mg/L; in steps S3 and S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, wherein ultrasonic treatment is carried out once every 2 hours, each ultrasonic treatment is carried out for 30 minutes, the ultrasonic frequency is 26KHz, and the ultrasonic power is 1200W.
Example 6:
different from the examples 4-5, in the step one, the stirring speed is 135RPM, the air input is 55ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 25; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 11; in the third step, the addition amount of the composite treating agent is as follows: 115 mg/L; in steps S3 and S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, ultrasonic treatment is carried out once every 1.5 hours, each ultrasonic treatment is carried out for 25 minutes, the ultrasonic frequency is 24KHz, and the ultrasonic power is 1100W.
Taking the method for treating semi-dry desulfurized fly ash prepared in the above examples 4-6, the method for treating semi-dry desulfurized fly ash of the control group seven, the method for treating semi-dry desulfurized fly ash of the control group eight, and the method for treating semi-dry desulfurized fly ash of the control group nine, respectively, the method for treating semi-dry desulfurized fly ash of the control group seven is compared with the method of example six, no ultrasonic treatment is performed in step S5, the method for treating semi-dry desulfurized fly ash of the control group eight is compared with the method of example six, no ultrasonic treatment is performed in step S3, the method for treating semi-dry desulfurized fly ash of the control group nine is compared with the method of example six, uninterrupted ultrasonic treatment is performed in step S3, the solid products prepared in the three examples and the solid products after treatment by the method for treating semi-dry desulfurized fly ash of the three control groups are tested in six groups, and the test results are shown in table two:
table two:
as can be seen from table two, example 6 is a preferred embodiment of the present invention; in step S3, performing ultrasonic treatment once every 1.5 hours, wherein the ultrasonic treatment is performed for 25 minutes each time, the ultrasonic frequency is 24KHz, the ultrasonic power is 1100W, and the mixture B generates a cavitation effect in the reaction kettle under the ultrasonic treatment, so that the reaction process inside the reaction kettle can be effectively enhanced, the material conversion can be promoted, the energy can be effectively saved by performing the intermittent operation, and meanwhile, the normal reaction inside the reaction kettle can be ensured, and the adverse effect of the ultrasonic treatment on the reaction process can be avoided; in step S5, at 24KHz and an ultrasonic power of 1100W, hydrazine hydrate and graphene oxide can be effectively and rapidly subjected to a contact reaction under ultrasonic treatment, and graphene oxide is reduced to form a composite material of graphene oxide and reduced graphene oxide.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for treating semi-dry desulfurized fly ash is characterized by comprising the following steps: the specific treatment steps are as follows:
the method comprises the following steps: adding metered desulfurized ash into an oxidation tank, adding water, stirring for 5-9 minutes, adding hydrogen peroxide, continuing stirring for 30-40 minutes, and introducing air into the bottom of the inner side of the oxidation tank during stirring to obtain slurry;
step two: pumping the slurry into a dehydrator by a slurry pump for dehydration to obtain a solid product and wastewater;
step three: adding a composite treating agent into the wastewater, continuously stirring for 30-40 minutes, simultaneously performing ultrasonic treatment for 5-10 minutes, and pumping the wastewater into a separation device through a wastewater pump to obtain separated water liquid and waste residues;
step four: the separated water liquid can be reused, and the separated waste residue is treated as hazardous waste.
2. The method for treating semi-dry desulfurized fly ash according to claim 1, wherein in the first step, the stirring speed is 130-140 RPM, the air inlet amount is 50-60 ml/min, and the ratio of the desulfurized fly ash to water by weight is: 1: 20-30; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 10-12; in the third step, the addition amount of the composite treating agent is as follows: 105-125 mg/L.
3. The method for treating semi-dry desulfurized fly ash according to claim 2, wherein: in the first step, the stirring speed is 130RPM, the air input is 50ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 20; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 10; in the third step, the addition amount of the composite treating agent is as follows: 105 mg/L.
4. The method for treating semi-dry desulfurized fly ash according to claim 2, wherein: in the first step, the stirring speed is 135RPM, the air input is 55ml/min, and the ratio of the desulfurized fly ash to the water by weight is as follows: 1: 25; the hydrogen peroxide and the desulfurized fly ash are in parts by weight: 1: 11; in the third step, the addition amount of the composite treating agent is as follows: 115 mg/L.
5. The method for treating semi-dry desulfurized fly ash according to claim 1, wherein: the composite treating agent in the first step comprises the following components in percentage by weight: 1.9-2.3% of graphene oxide, 2.8-3.2% of potassium manganate, 2.8-3.2% of aluminum nitrate, 2.9-3.5% of silver nitrate, 3.1-3.5% of zinc nitrate, 2.3-2.5% of sodium hydroxide, 16.6-17.2% of hydrazine hydrate and the balance of straw;
the preparation process of the composite treating agent comprises the following specific preparation steps:
s1: weighing graphene oxide, potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, straws, sodium hydroxide and hydrazine hydrate according to the weight percentage;
s2: firstly stirring and dissolving potassium manganate, aluminum nitrate, silver nitrate, zinc nitrate, sodium hydroxide and two-thirds by weight of hydrazine hydrate in deionized water to obtain a mixed solution A, then dissolving crushed straws in the mixed solution A, and stirring for 1-2 hours to obtain a mixed material B;
s3: adding the mixture B into a reaction kettle, reacting at 180-230 ℃ for 12-15 h, simultaneously carrying out ultrasonic treatment to obtain a solid product, washing the solid product with deionized water at room temperature, and drying at 108-112 ℃;
s4: heating the solid product dried in the step S3 to 700-780 ℃ under activated gas, keeping the temperature for 2.5-3.5 h, and cooling to obtain a mixture C;
s5: and (4) uniformly mixing the mixture C with the graphene oxide and the residual hydrazine hydrate in the step S1, adding the mixture C into deionized water, carrying out ultrasonic treatment for 10-20 minutes, and dehydrating and drying to obtain the composite treating agent.
6. The method for treating semi-dry desulfurized fly ash according to claim 5, wherein: the composite treating agent comprises the following components in percentage by weight: 1.9% of graphene oxide, 2.8% of potassium manganate, 2.8% of aluminum nitrate, 2.9% of silver nitrate, 3.1% of zinc nitrate, 2.3% of sodium hydroxide, 16.6% of hydrazine hydrate and 67.6% of straws.
7. The method for treating semi-dry desulfurized fly ash according to claim 5, wherein: the composite treating agent comprises the following components in percentage by weight: 2.3% of graphene oxide, 3.2% of potassium manganate, 3.2% of aluminum nitrate, 3.5% of silver nitrate, 3.5% of zinc nitrate, 2.5% of sodium hydroxide, 17.2% of hydrazine hydrate and 64.6% of straws.
8. The method for treating semi-dry desulfurized fly ash according to claim 5, wherein: the composite treating agent comprises the following components in percentage by weight: 2.1% of graphene oxide, 3.0% of potassium manganate, 3.0% of aluminum nitrate, 3.2% of silver nitrate, 3.3% of zinc nitrate, 2.4% of sodium hydroxide, 16.9% of hydrazine hydrate and 66.1% of straws.
9. The method for treating semi-dry desulfurized fly ash according to claim 5, wherein: in the step S3 and the step S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, the ultrasonic treatment is carried out once every 1-2 hours, each ultrasonic treatment is carried out for 20-30 minutes, the ultrasonic frequency is 22-26 KHz, and the ultrasonic power is 1000-1200W.
10. The method for treating semi-dry desulfurized fly ash according to claim 9, wherein: in steps S3 and S5, the ultrasonic treatment process adopts intermittent ultrasonic treatment, ultrasonic treatment is carried out once every 1.5 hours, each ultrasonic treatment is carried out for 25 minutes, the ultrasonic frequency is 24KHz, and the ultrasonic power is 1100W.
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