CN116689461A - Industrial organic waste salt oxidation treatment method - Google Patents
Industrial organic waste salt oxidation treatment method Download PDFInfo
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- CN116689461A CN116689461A CN202310673439.XA CN202310673439A CN116689461A CN 116689461 A CN116689461 A CN 116689461A CN 202310673439 A CN202310673439 A CN 202310673439A CN 116689461 A CN116689461 A CN 116689461A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 101
- 230000003647 oxidation Effects 0.000 title claims abstract description 50
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 50
- 239000010815 organic waste Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000002002 slurry Substances 0.000 claims abstract description 42
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 28
- 239000011572 manganese Substances 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 claims abstract description 28
- 239000002699 waste material Substances 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- -1 allyl betacyclodextrin Chemical compound 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- 239000003960 organic solvent Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000858 Cyclodextrin Polymers 0.000 claims description 15
- 239000001116 FEMA 4028 Substances 0.000 claims description 15
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 15
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 15
- 229960004853 betadex Drugs 0.000 claims description 15
- 239000011565 manganese chloride Substances 0.000 claims description 15
- 229940099607 manganese chloride Drugs 0.000 claims description 15
- 235000002867 manganese chloride Nutrition 0.000 claims description 15
- VEDYBWCXQCEXEB-UHFFFAOYSA-N cyclopenta-2,4-dien-1-amine iron(2+) Chemical compound [Fe++].N[c-]1cccc1.N[c-]1cccc1 VEDYBWCXQCEXEB-UHFFFAOYSA-N 0.000 claims description 14
- WBGTUUOKNJTUDK-UHFFFAOYSA-N ethane-1,2-diamine;hydrobromide Chemical compound Br.NCCN WBGTUUOKNJTUDK-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000005273 aeration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical group [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 239000002440 industrial waste Substances 0.000 description 13
- 150000004696 coordination complex Chemical class 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical group Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000012747 synergistic agent Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/35—Shredding, crushing or cutting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
- B09B3/38—Stirring or kneading
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
Abstract
The invention discloses an industrial organic waste salt oxidation treatment method, and belongs to the field of organic waste salt treatment. Grinding organic waste salt into powder, adding the powder into water, stirring and mixing uniformly to prepare slurry, regulating the pH value of the slurry by using a pH regulator, introducing an oxidant into an oxidation reactor for reaction, cooling, discharging and filtering out insoluble salt after the reaction is finished, evaporating and crystallizing filtrate to obtain recovered salt, and thus, the oxidation treatment of the industrial machine waste salt can be finished. The invention also adopts the manganese/ferrocene organic metal framework material synergist, can basically remove organic matters in a high-temperature calcination working section, and has the characteristics of easy realization of reaction catalytic reaction, simple process, reliable technology, no increase of three-waste emission and high economic benefit.
Description
Technical Field
The invention relates to the field of organic waste salt treatment, in particular to an industrial organic waste salt oxidation treatment method.
Background
The industrial waste salt mainly comes from organic matters, other toxic salt-containing waste liquid and solid industrial waste salt generated in the chemical industry, pharmacy, agriculture and coal chemical industry production processes, and the main salt production links include reaction salt generated by mother liquor (process waste water), neutralization salt generated by acid-base chemical reaction, salting-out salt, salt mud generated by distillation residual liquid and the like. The organic matters in the waste salt have complex composition, and have the characteristics of various kinds, complex components, numerous sources, high treatment cost, great environmental hazard and the like. In recent years, the production of waste salt in China is continuously increased, and the annual production is estimated to exceed 3000 ten thousand tons.
In 2021, "national hazardous waste List", the wastes such as distillation and reaction residues, waste mother liquor, reaction tank and container cleaning waste liquid in various production processes are formally listed in the hazardous waste List. If the waste salt is improperly treated, the pollution of surface water, underground water and soil can be directly caused. At present, waste salt is generally processed in a mode of centralized temporary storage in a warehouse, high storage and management cost is faced, enterprises are hard to bear, and the problem of 'neck clamping' which restricts the development of the enterprises is already caused. Meanwhile, industrial waste salt is also an important chemical raw material, if the industrial waste salt can be recycled as industrial raw material salt, not only can the pollution of the industrial raw material salt to the environment be eliminated, but also salt resources can be fully utilized, and the recycling and cyclic utilization of the byproduct salt can be realized. Under the background, the harmless and recycling comprehensive utilization of the waste salt becomes a necessary way for disposing the waste salt, and factors restricting the large-scale development of the waste salt mainly remove organic matters in the waste salt.
The patent relates to a harmless treatment and recycling method of industrial waste salt (application number: CN 202210697600.2), which comprises the steps of firstly, conveying the industrial waste salt into a thermal analysis unit by adopting a dry feeding unit, heating the industrial waste salt to 300-600 ℃, evaporating water in the industrial waste salt, decomposing macromolecular organic matters by heating, producing a high-temperature gaseous mixture, spraying, cooling and purifying to obtain a boiler fuel, and taking high-temperature steam produced by the boiler as a heat source of an evaporation crystallization unit; dissolving solid slag produced by pyrolysis, performing filter pressing, removing impurities from the obtained liquid, sending the liquid into an evaporation crystallization unit to obtain industrial refined salt, condensing the evaporated water, and returning the condensed water to a boiler or using the condensed water as circulating water.
The patent No. CN202210434295.8 is to oxidize organic matters in industrial waste salt, decompose harmlessly, melt soluble alkali metal salt, alkaline earth metal salt, heavy metal and conversion assistant components, form crystal, melt, mineralize precursor, form solid solution, form low temperature eutectic, quench and cool the liquid melt to obtain compact solid solution product; the toxic organic matters in the industrial waste salt are thoroughly and harmlessly decomposed at high temperature, precursors synthesized by toxic matters of dioxin POPs which cannot be avoided by conventional high-temperature treatment are eliminated from the source, and soluble inorganic salt components and heavy metals in the industrial waste salt are sealed in a compact solid solution material network structure, so that no risk of dissolution exists, and the method can be used for recycling.
At present, the industrial waste salt is mainly treated in a high-temperature incineration mode, and the temperature of a high-temperature calcination working section can only be controlled to be 500-600 ℃ due to the limitation of the melting point of the waste salt, so that partial organic matters which are not easy to decompose can be remained in salt residues after the waste salt is calcined. Part of the organic matters can not be removed in the high-temperature calcination working section due to uneven heating in the calciner.
Disclosure of Invention
In order to solve at least one problem in the background technology, the invention provides an oxidation treatment method for industrial organic waste salt, which uses an oxidant to remove the industrial organic waste salt through oxidation treatment, has simple process, is green and environment-friendly, and does not increase the discharge of three wastes.
An oxidation treatment method of industrial organic waste salt comprises the following steps:
according to the parts by weight, 100-180 parts of low-content organic waste salt is put into a grinder, ground into powder of 20-80 meshes, then added into 140-200 parts of water, stirred and mixed uniformly to prepare slurry, and then the pH value of the slurry is regulated by a pH regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 30-60min; and after the slurry is added, continuing to react for 20-30min to complete the reaction, discharging after the completion, cooling to 20-30 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and thus finishing the oxidation treatment of the industrial machine waste salt.
The preferable technical scheme is as follows: the pH value regulator is sodium hydroxide or sulfuric acid solution with the mass percentage concentration of 10-20%.
The preferable technical scheme is as follows: the pH value is controlled to be 3-5.
The preferable technical scheme is as follows: the oxidizing agent is selected from ozone or hydrogen peroxide gas or oxygen.
The preferable technical scheme is as follows: the aeration rate of the oxidant is 10-18 g/h.L.
The preferable technical scheme is as follows: the reaction temperature of the oxidation reactor is 40-60 ℃.
The preferable technical scheme is as follows: the oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material, an allyl betacyclodextrin and manganese chloride are used for generating a metal complex, and then the metal complex is subjected to amino-alkene addition reaction with 1,1' -diaminoferrocene and 0.5-3.3 parts of ethylenediamine hydrobromide, so that the oxidation synergist is prepared
The preferable technical scheme is as follows: the preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: according to the mass parts, adding 5-10 parts of allyl betacyclodextrin, 1-3 parts of manganese chloride and 100-120 parts of organic solvent into a stirring kettle, and stirring for reaction for 30-60min;
step 2: adding 0.005-0.06 part of 1,1' -diaminoferrocene, 0.5-3.3 parts of ethylenediamine hydrobromide and 2-5 parts of potassium hydroxide, stirring and reacting for 100-150min, and distilling to remove the organic solvent;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 10-15 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
The preferable technical scheme is as follows: the organic solvent is selected from ethanol, dimethylformamide, acetone, chloroform or cyclohexane.
The preferable technical scheme is as follows: the reaction temperature of the step 1 is 25-35 ℃, the reaction temperature of the step 2 is 50-65 ℃, and the reaction temperature of the step 3 is 100-110 ℃.
The reaction mechanism is as follows:
in the reaction system, the manganese-containing metal complex can provide the required oxygen atoms, thereby generating a manganese oxide catalyst and free radicals. Then, ferrocene can be used as an electron transfer reagent to participate in electron transfer of a reaction system, so that free radical generation is promoted. The hydrobromide functional group can react with organic molecules in the waste salt, so that the substitution degree of the organic molecules and the electrophilicity of reactants are increased, and the activation of the catalyst is accelerated, thereby enabling the whole oxidation treatment reaction to be more efficient.
Compared with the prior art, the invention has the following technical effects: because of the limitation of the melting point of the waste salt, the temperature of the high-temperature calcination working section can only be controlled to be 500-600 ℃, so that partial organic matters which are not easy to decompose can be remained in the salt slag after the waste salt is calcined. Part of the organic matters can not be removed in the high-temperature calcination working section due to uneven heating in the calciner. The invention adopts the manganese/ferrocene organic metal framework material synergist, and can basically remove organic matters in a high-temperature calcination working section.
Detailed Description
The above-described aspects are further described below in conjunction with specific embodiments. It is to be understood that these examples are for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention, but are intended to cover all equivalent changes or modifications which are within the spirit of the invention. The implementation conditions used in the examples may be further adjusted according to the conditions of the specific manufacturer, and the implementation conditions not specified are generally those in routine experiments.
Example 1:
an oxidation treatment method of industrial organic waste salt comprises the following steps:
100kg of low-content organic waste salt is put into a grinder, ground into 45-mesh powder, then added into 140kg of water, stirred and mixed uniformly to prepare slurry, and then the pH value of the slurry is regulated by a pH regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 30min; and (3) continuing to react for 20 minutes after the slurry is added, finishing the reaction, discharging after finishing, cooling to 20 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and finishing the oxidation treatment of the waste salt of the industrial machine.
The pH value is controlled at 3.
The oxidizing agent is selected from ozone.
The aeration rate of the oxidant is 10 g/h.L.
The reaction temperature of the oxidation reactor is 40 ℃.
The oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material, and the synergist is prepared by generating a metal complex through allyl betacyclodextrin and manganese chloride and then generating amino-alkene addition reaction with 1,1' -diamino ferrocene and ethylenediamine hydrobromide
The preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: adding 5kg of allyl betacyclodextrin, 1kg of manganese chloride and 100kg of organic solvent into a stirring kettle, and stirring for reaction for 30min;
step 2: adding 0.01kg of 1,1' -diaminoferrocene, 0.5kg of ethylenediamine hydrobromide and 2kg of potassium hydroxide, stirring and reacting for 100min, and distilling to remove the organic solvent;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
The organic solvent is selected from ethanol.
The reaction temperature of the step 1 is 25 ℃, the reaction temperature of the step 2 is 50 ℃, and the reaction temperature of the step 3 is 100 ℃.
Example 2
An oxidation treatment method of industrial organic waste salt comprises the following steps:
putting 135kg of low-content organic waste salt into a grinder, grinding into 40-mesh powder, adding into 160kg of water, stirring and mixing uniformly to prepare slurry, and adjusting the pH value of the slurry to 3 by using a pH value regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 40min; and (3) continuing to react for 20 minutes after the slurry is added, finishing the reaction, discharging after finishing, cooling to 20 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and finishing the oxidation treatment of the waste salt of the industrial machine.
The pH value is controlled at 3.
The oxidizing agent is selected from hydrogen peroxide gas.
The aeration rate of the oxidant is 12 g/h.L.
The reaction temperature of the oxidation reactor is 45 ℃.
The oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material, and the synergist is prepared by generating a metal complex through allyl betacyclodextrin and manganese chloride and then generating amino-alkene addition reaction with 1,1' -diamino ferrocene and ethylenediamine hydrobromide
The preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: adding 6kg of allyl betacyclodextrin, 2kg of manganese chloride and 100kg of organic solvent into a stirring kettle, and stirring for reaction for 40min;
step 2: 0.035kg of 1,1' -diaminoferrocene, 1.2kg of ethylenediamine hydrobromide and 3kg of potassium hydroxide are added, stirred and reacted for 115min, and the organic solvent is distilled off;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 12 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
The organic solvent is selected from ethanol, dimethylformamide, acetone, chloroform or cyclohexane.
The reaction temperature of the step 1 is 25 ℃, the reaction temperature of the step 2 is 55 ℃, and the reaction temperature of the step 3 is 100 ℃.
Example 3
An oxidation treatment method of industrial organic waste salt comprises the following steps:
placing 150kg of low-content organic waste salt into a grinder, grinding into 60-mesh powder, adding into 180kg of water, stirring and mixing uniformly to prepare slurry, and adjusting the pH value of the slurry to 4 by using a pH value regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 50min; and (3) continuing to react for 25 minutes after the slurry is added, finishing the reaction, discharging after finishing, cooling to 25 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and finishing the oxidation treatment of the waste salt of the industrial machine.
The pH value is controlled at 4.
The oxidant is selected from oxygen.
The aeration rate of the oxidant is 16 g/h.L.
The reaction temperature of the oxidation reactor is 55 ℃.
The oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material, and the synergist is prepared by generating a metal complex through allyl betacyclodextrin and manganese chloride and then generating amino-alkene addition reaction with 1,1' -diamino ferrocene and ethylenediamine hydrobromide
The preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: 8kg of allyl betacyclodextrin, 2kg of manganese chloride and 110kg of organic solvent are added into a stirring kettle for stirring reaction for 50min;
step 2: 0.045kg of 1,1' -diaminoferrocene, 2.3kg of ethylenediamine hydrobromide and 4kg of potassium hydroxide are added, stirred and reacted for 135min, and the organic solvent is distilled off;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 14 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
The organic solvent is selected from ethanol, dimethylformamide, acetone, chloroform or cyclohexane.
The reaction temperature in the step 1 is 30 ℃, the reaction temperature in the step 2 is 60 ℃, and the reaction temperature in the step 3 is 110 ℃.
Example 4
An oxidation treatment method of industrial organic waste salt comprises the following steps:
180kg of low-content organic waste salt is put into a grinder, ground into 80-mesh powder, then added into 200kg of water, stirred and mixed uniformly to prepare slurry, and then the pH value of the slurry is adjusted to 5 by using a pH value regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 60min; and (3) continuing to react for 30min after the slurry is added, completing the reaction, discharging after the completion, cooling to 30 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and thus completing the oxidation treatment of the waste salt of the industrial machine.
The pH value is controlled at 5.
The oxidizing agent is selected from ozone.
The aeration rate of the oxidant is 18 g/h.L.
The reaction temperature of the oxidation reactor is 60 ℃.
The oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material, and the synergist is prepared by generating a metal complex through allyl betacyclodextrin and manganese chloride and then generating amino-alkene addition reaction with 1,1' -diamino ferrocene and ethylenediamine hydrobromide
The preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: adding 10kg of allyl betacyclodextrin, 3kg of manganese chloride and 120kg of organic solvent into a stirring kettle, and stirring and reacting for 60min;
step 2: adding 0.06kg of 1,1' -diaminoferrocene, 3.3kg of ethylenediamine hydrobromide and 5kg of potassium hydroxide, stirring and reacting for 150min, and distilling to remove the organic solvent;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 15 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
The organic solvent is selected from ethanol, dimethylformamide, acetone, chloroform or cyclohexane.
The reaction temperature in the step 1 is 35 ℃, the reaction temperature in the step 2 is 65 ℃, and the reaction temperature in the step 3 is 110 ℃.
Comparative example 1
An oxidation treatment method of industrial organic waste salt comprises the following steps:
100kg of low-content organic waste salt is put into a grinder, ground into 45-mesh powder, then added into 140kg of water, stirred and mixed uniformly to prepare slurry, and then the pH value of the slurry is regulated by a pH regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 30min; and (3) continuing to react for 20 minutes after the slurry is added, finishing the reaction, discharging after finishing, cooling to 20 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and finishing the oxidation treatment of the waste salt of the industrial machine.
The pH value is controlled at 3.
The oxidizing agent is selected from ozone.
The aeration rate of the oxidant is 10 g/h.L.
The reaction temperature of the oxidation reactor is 40 ℃.
The oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material, and the synergist is prepared by generating a metal complex through allyl betacyclodextrin and manganese chloride and then generating amino-alkene addition reaction with 1,1' -diamino ferrocene and ethylenediamine hydrobromide
The preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: adding 5kg of allyl betacyclodextrin, 1kg of manganese chloride and 100kg of organic solvent into a stirring kettle, and stirring for reaction for 30min;
step 2: adding 0.01kg of 1,1' -diaminoferrocene and 2kg of potassium hydroxide, stirring and reacting for 100min, and distilling to remove the organic solvent;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
The organic solvent is selected from ethanol.
The reaction temperature of the step 1 is 25 ℃, the reaction temperature of the step 2 is 50 ℃, and the reaction temperature of the step 3 is 100 ℃.
Comparative example 2
An oxidation treatment method of industrial organic waste salt comprises the following steps:
100kg of low-content organic waste salt is put into a grinder, ground into 45-mesh powder, then added into 140kg of water, stirred and mixed uniformly to prepare slurry, and then the pH value of the slurry is regulated by a pH regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 30min; and (3) continuing to react for 20 minutes after the slurry is added, finishing the reaction, discharging after finishing, cooling to 20 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and finishing the oxidation treatment of the waste salt of the industrial machine.
The pH value is controlled at 3.
The oxidizing agent is selected from ozone.
The aeration rate of the oxidant is 10 g/h.L.
The reaction temperature of the oxidation reactor is 40 ℃.
The oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material, and the synergist is prepared by generating a metal complex through allyl betacyclodextrin and manganese chloride and then generating amino-alkene addition reaction with 1,1' -diamino ferrocene and ethylenediamine hydrobromide
The preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: adding 5kg of allyl betacyclodextrin, 1kg of manganese chloride and 100kg of organic solvent into a stirring kettle, and stirring for reaction for 30min;
step 2: adding 0.5kg of ethylenediamine hydrobromide and 2kg of potassium hydroxide, stirring and reacting for 100min, and distilling to remove the organic solvent;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 10 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
The organic solvent is selected from ethanol.
The reaction temperature of the step 1 is 25 ℃, the reaction temperature of the step 2 is 50 ℃, and the reaction temperature of the step 3 is 100 ℃.
The effect of the above examples is compared with that of the comparative examples:
the above treated industrial organic waste salt was subjected to component detection, and the results were as follows:
as can be seen from the comprehensive analysis of the data of the examples and the comparative examples, the method can effectively remove the organic matters in the industrial waste salt, and the TOD content can be reduced to below 10mg/L to reach the standard range. The manganese/ferrocene organic metal framework material synergistic agent is adopted, so that organic matters can be basically removed in a high-temperature calcination working section.
Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (10)
1. An oxidation treatment method of industrial organic waste salt comprises the following steps:
according to the parts by weight, 100-180 parts of low-content organic waste salt is put into a grinder, ground into powder of 20-80 meshes, then added into 140-200 parts of water, stirred and mixed uniformly to prepare slurry, and then the pH value of the slurry is regulated by a pH regulator; slowly adding the prepared slurry into an oxidation reactor and introducing an oxidant, wherein the slurry adding time is 30-60min; and after the slurry is added, continuing to react for 20-30min to complete the reaction, discharging after the completion, cooling to 20-30 ℃, filtering out insoluble salt, evaporating and crystallizing the filtrate to obtain recovered salt, and thus finishing the oxidation treatment of the industrial machine waste salt.
2. The method for oxidizing industrial organic waste salt according to claim 1, wherein: the pH value regulator is sodium hydroxide or sulfuric acid solution with the mass percentage concentration of 10-20%.
3. The method for oxidizing industrial organic waste salt according to claim 1, wherein: the pH value is controlled to be 3-5.
4. The method for oxidizing industrial organic waste salt according to claim 1, wherein: the oxidizing agent is selected from ozone or hydrogen peroxide gas or oxygen.
5. The method for oxidizing industrial organic waste salt according to claim 1, wherein: the aeration rate of the oxidant is 10-18 g/h.L.
6. The method for oxidizing industrial organic waste salt according to claim 1, wherein: the reaction temperature of the oxidation reactor is 40-60 ℃.
7. The method for oxidizing industrial organic waste salt according to claim 1, wherein: the oxidation reactor contains a synergist which is manganese/ferrocene organic metal framework material.
8. The method for oxidizing industrial organic waste salt according to claim 7, wherein: the preparation method of the synergist manganese/ferrocene organic metal framework material comprises the following steps:
step 1: according to the mass parts, adding 5-10 parts of allyl betacyclodextrin, 1-3 parts of manganese chloride and 100-120 parts of organic solvent into a stirring kettle, and stirring for reaction for 30-60min;
step 2: adding 0.005-0.06 part of 1,1' -diaminoferrocene, 0.5-3.3 parts of ethylenediamine hydrobromide and 2-5 parts of potassium hydroxide, stirring and reacting for 100-150min, and distilling to remove the organic solvent;
step 3: then transferring the mixture into a polytetrafluoroethylene reaction kettle, reacting for 10-15 hours at constant temperature, taking out, cooling to room temperature, and drying to obtain the manganese/ferrocene organic metal framework material.
9. The method for oxidizing industrial organic waste salt according to claim 8, wherein: the organic solvent is selected from ethanol, dimethylformamide, acetone, chloroform or cyclohexane.
10. The method for oxidizing industrial organic waste salt according to claim 8, wherein: the reaction temperature of the step 1 is 25-35 ℃, the reaction temperature of the step 2 is 50-65 ℃, and the reaction temperature of the step 3 is 100-110 ℃.
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