CN113429139B - Method for cooperatively treating fluorine-containing inorganic compound by cement kiln - Google Patents
Method for cooperatively treating fluorine-containing inorganic compound by cement kiln Download PDFInfo
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- 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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0836—Compounds with one or more Si-OH or Si-O-metal linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/11—Compounds covalently bound to a solid support
Abstract
The invention relates to the field of waste treatment, and discloses a method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln, which comprises the following steps: preparing a fluorine decomposition curing agent, performing synergistic treatment, treating and the like; the invention can fully finish the decomposition of organic fluorine-containing compounds in fluorine-containing inorganic compounds, and completely fix fluorine elements in solid materials, does not generate fluoride smoke dust, and does not worry about secondary pollution; the method of the invention fully combines the characteristic of high residual heat of the cement kiln, completely utilizes the residual heat of the cement kiln to carry out harmless treatment on all fluorine-containing inorganic compounds, and utilizes the residual inorganic waste residue as the raw material of the cement kiln for secondary utilization, thereby conforming to the development trend of current circular economy and green economy.
Description
Technical Field
The invention relates to the field of waste treatment, in particular to a method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln.
Background
Fluorine and inorganic compounds thereof are widely used in the chemical industry for manufacturing medicines, pesticides, refrigerants, wood preservatives, organic reaction catalysts, fluoroplastics, fluororubbers and the like; fluorine and most inorganic fluorides are primary stimulants and have different degrees of stimulation on skin, respiratory tract and gastrointestinal mucosa.
CN102897829B environmental protection treatment of fluorine-containing and potassium-containing waste to produce potassium fluotitanate, fluorine-containing waste liquid and potassium liquid are added with titanium ore of theoretical amount in stirring to prepare iron fluotitanate slurry; adding the clear liquid obtained after filter pressing of the potassium-containing waste residues or waste liquid into the iron fluotitanate clear liquid in a metering way to react to prepare potassium fluotitanate; performing liquid-solid separation, washing and drying on potassium fluotitanate slurry, adding lime into waste residues and waste water to adjust the pH value, performing filter pressing to obtain filter residues, adding an oxidant into the filtrate in a degradation tank, irradiating the filtrate for 1 to 5 hours by using ultraviolet light, detecting COD (chemical oxygen demand) and analyzing F-. The invention uses waste materials containing fluorine and potassium to replace hydrogen fluoride and imported potassium chloride to produce potassium fluotitanate, changes waste into valuable, has the recovery rate of fluorine, titanium and potassium which is not much different from that of the used raw materials of the quality products, fully utilizes fluorine and potassium, can obtain the potassium fluotitanate with lower production cost, and solves the problem of environmental pollution caused by the waste materials containing fluorine and potassium.
CN108602096A discloses a treatment of solid waste containing fluorine compounds and various applications thereof. The method for treating solid waste containing fluorine compounds comprises the following steps: providing and mixing (i) fluorochemical waste and (ii) solid calcium hydroxide to form a mixture thereof; heating the mixture in a chemically reducing (non-oxidizing) environment to form a heated product comprising solid calcium fluoride; and treating or/and processing the heated product to form a non-hazardous, safe, disposable material. A solid waste treatment system comprising: a solid waste input unit; a solid calcium hydroxide supply unit; a mixing unit; a heating unit; and a product treatment/product processing unit. The invention is applicable to large scale commercial processing, or products and materials related to, making, and generating large quantities of fluorochemical solid waste during their processing, and thus the need to treat or/and process and dispose of such solid waste.
CN105152619A provides a processing method of fluorine-containing hazardous waste, which comprises the following steps: step one, taking fluorine-containing hazardous waste to be treated, and detecting the fluorine content of a leaching solution of the fluorine-containing hazardous waste; and step two, determining the content of a corresponding treatment agent according to the fluorine content of the leaching solution of the fluorine-containing hazardous waste, and step three, adding the treatment agent into the fluorine-containing hazardous waste, adding water, uniformly mixing, standing, and fully reacting to complete the treatment of the fluorine-containing hazardous waste. The invention also discloses a formula of a treatment agent in the treatment method of the fluorine-containing hazardous waste. Compared with the related art, the invention has the advantages of low treatment cost; the operation is simple; the treatment process and the treatment process do not cause secondary pollution.
Landfill is the main method to treat the fluorine-containing solid waste at present, but will withdraw from the market gradually under the situation that the environmental regulation is stricter and the land resource is more and more precious at present; the incineration method for treating the fluorine-containing inorganic compound not only consumes a large amount of energy, but also causes secondary pollution of fluoride smoke dust and causes public safety accidents.
Disclosure of Invention
In order to solve the problems, the invention provides a method for cooperatively treating fluorine-containing inorganic compounds by using a cement kiln.
A method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln comprises the following steps:
preparation of fluorine decomposition curing agent: according to the mass parts, 23-48 parts of neodymium iron boron waste, 32-64 parts of vanadium-titanium-containing slag, 5-15 parts of iron-doped titanium dioxide, 18-28 parts of electrolytic manganese-containing waste residue, 8-24 parts of blast furnace slag and 2-8 parts of molten copper slag are added into a grinding machine and ground into powder of 80-160 meshes; then adding the powder into 300-400 parts of acid solution with the molar concentration of 0.5-4mol/L, uniformly mixing, putting the material into a ball mill, carrying out ball milling for 2-5h, and filtering and separating to obtain activated slag powder; then adding the mixture into 1500-2800 parts of soda lime, and stirring and mixing uniformly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 100-180 parts of fluorine-containing inorganic compound and 30-80 parts of fluorine decomposition curing agent to obtain a mixed material, feeding the mixed material into drying equipment, drying and dewatering at 80-100 ℃, and then conveying the mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides hot air at the temperature of 500-600 ℃ in a cement kiln decomposition system into the treatment equipment to heat the mixed material, and the reaction time is 30-90 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
The preparation method of the iron-doped titanium dioxide comprises the following steps:
adding 20-30 parts of titanium dioxide into 300 parts of white oil 200-fold, adding 2-5 parts of a compound with sulfydryl and silicon base, introducing nitrogen, stirring and reacting at 30-50 ℃ for 30-60min, then adding 3.5-6.5 parts of ferric acrylate, 0.12-0.25 part of 2-methoxy-6-vinyl phenylboronic acid and 2.2-3.6 parts of sodium methoxide, slowly adding into a reaction kettle, heating to 50-62 ℃, stirring and reacting for 100-fold for 300min, filtering, and drying to obtain the iron-doped titanium dioxide.
The compound with mercapto and silicon group is selected from gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane and mercaptomethyltriethoxysilane.
The iron-doped titanium dioxide is subjected to surface treatment by adopting mercapto-group and silicon-based compounds, and then undergoes Michael addition reaction with iron acrylate and 2-methoxy-6-vinyl phenylboronic acid under the catalysis of sodium methoxide, wherein the chemical equation of the partial reaction is as follows:
and
the acid solution is oxalic acid solution or formic acid solution or acetic acid solution.
The mixed material is stirred once in a device for processing 2-5 min.
The hot air in the heat treatment equipment is not directly contacted with the mixture.
The pressure in the heat treatment equipment is 0.2-1.6 MPa.
The treatment temperature of the mixed material in the treatment equipment is 350-550 ℃.
The invention discloses a method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln, which comprises the steps of firstly, carrying out surface treatment on titanium dioxide by using various slag and waste residues containing heavy metals and iron-doped titanium dioxide, carrying out Michael addition reaction on the iron-doped titanium dioxide and the titanium dioxide by adopting mercapto and silicon-based compounds, then, carrying out activation treatment on the obtained iron-doped titanium dioxide and adding the obtained titanium dioxide into soda lime to prepare a fluorine decomposition curing agent, then, mixing the fluorine decomposition curing agent and the fluorine-containing inorganic compounds, drying, decomposing and absorbing the mixture by using the heat of the cement kiln, fully decomposing organic fluorine-containing compounds in the fluorine-containing inorganic compounds, completely fixing fluorine elements in solid materials without generating fluoride smoke dust, secondary pollution is not worried about; the method of the invention fully combines the characteristic of high residual heat of the cement kiln, completely utilizes the residual heat of the cement kiln to carry out harmless treatment on all fluorine-containing inorganic compounds, and utilizes the residual inorganic waste residue as the raw material of the cement kiln for secondary utilization.
Drawings
FIG. 1 is a Fourier infrared spectrum of iron-doped titanium dioxide prepared in example 3:
the absorption peak of titanium dioxide exists near 494cm-1, and the absorption peak of hydroxyl exists near 2946cm-1, which indicates that titanium dioxide participates in the reaction; an antisymmetric telescopic absorption peak of carboxylate ions exists near 1610cm < -1 >, and a telescopic absorption peak of carbon-hydrogen bonds exists near 2856cm < -1 >, so that the iron acrylate participates in the reaction; a symmetrical stretching absorption peak of a silicon-oxygen bond exists near 793cm < -1 >, a stretching absorption peak of a silicon-carbon bond exists near 690cm < -1 >, and a stretching absorption peak of a carbon-sulfur bond exists near 740cm < -1 >, so that the gamma-mercaptopropyltrimethoxysilane participates in the reaction; an expansion and contraction absorption peak of a benzene ring skeleton exists near 1500cm < -1 >, an expansion and contraction absorption peak of a carbon-oxygen bond exists near 1298cm < -1 >, and an absorption peak of a boron-oxygen bond exists near 1342cm < -1 >, which indicates that the 2-methoxy-6-vinyl phenylboronic acid participates in the reaction.
Detailed Description
The invention is further illustrated by the following specific examples:
example 1
A method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln comprises the following steps:
step one, preparing a fluorine decomposition curing agent: adding 23kg of neodymium iron boron waste, 32kg of vanadium-titanium-containing slag, 5kg of iron-doped titanium dioxide, 18kg of electrolytic manganese-containing waste slag, 8kg of blast furnace slag and 2kg of molten copper slag into a grinding machine, and grinding into 80-mesh powder; then adding the powder into 300kg of acid solution with the molar concentration of 0.5mol/L, uniformly mixing, putting the material into a ball mill, carrying out ball milling for 2 hours, and filtering and separating to obtain activated slag powder; then adding the mixture into 1500kg of soda lime, and stirring and mixing the mixture evenly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 100kg of fluorine-containing inorganic compound and 30kg of fluorine decomposition curing agent to obtain a mixed material, conveying the mixed material into drying equipment, drying and dewatering at 80 ℃, and conveying the mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides hot air at 500 ℃ in a cement kiln decomposition system into processing equipment to heat the mixed material, and the reaction time is 30 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
The preparation method of the iron-doped titanium dioxide comprises the following steps:
adding 20kg of titanium dioxide into 200kg of white oil, adding 2kg of compound with sulfydryl and silicon base, introducing nitrogen, stirring and reacting for 30min at 30 ℃, then adding 3.5kg of ferric acrylate, 0.12kg of 2-methoxy-6-vinyl phenylboronic acid and 2.2kg of sodium methoxide, slowly adding the mixture into a reaction kettle, heating to 50 ℃, stirring and reacting for 100min, filtering and drying to obtain the iron-doped titanium dioxide.
The compound with mercapto and silicon group is selected from gamma-mercapto propyl trimethoxy silane.
The acid solution is oxalic acid solution.
The mixed materials are stirred once in a device for processing 2 min.
The hot air in the heat treatment equipment is not directly contacted with the mixture.
The pressure in the heat treatment equipment is 0.2 MPa.
The processing temperature of the mixed material in the processing equipment is 350 ℃.
Example 2
A method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln comprises the following steps:
step one, preparing a fluorine decomposition curing agent: adding 36kg of neodymium iron boron waste, 48kg of vanadium-titanium-containing slag, 10kg of iron-doped titanium dioxide, 23kg of electrolytic manganese-containing waste slag, 16kg of blast furnace slag and 5kg of molten copper slag into a grinding machine, and grinding into 120-mesh powder; then adding the powder into 350kg of acid solution with the molar concentration of 2.3mol/L, uniformly mixing, putting the material into a ball mill, carrying out ball milling for 4 hours, and filtering and separating to obtain activated slag powder; then adding the mixture into 2200kg of soda lime, and stirring and mixing uniformly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 140kg of fluorine-containing inorganic compound and 50kg of fluorine decomposition curing agent to obtain a mixed material, conveying the mixed material into drying equipment, drying at 90 ℃ to remove water, and conveying the dried mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides 550 ℃ hot air in the cement kiln decomposition system into the treatment equipment to heat the mixed material, and the reaction time is 60 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
The preparation method of the iron-doped titanium dioxide comprises the following steps:
adding 25kg of titanium dioxide into 250kg of white oil, adding 4kg of compound with sulfydryl and silicon base, introducing nitrogen, stirring and reacting for 45min at 40 ℃, then adding 5kg of ferric acrylate, 0.19kg of 2-methoxy-6-vinyl phenylboronic acid and 2.9kg of sodium methoxide, slowly adding the mixture into a reaction kettle, heating to 56 ℃, stirring and reacting for 200min, filtering, and drying to obtain the iron-doped titanium dioxide.
The compound with sulfydryl and silicon base is selected from gamma-mercaptopropylmethyldimethoxysilane.
The acid solution is formic acid solution.
The mixed materials are stirred once in a device for processing 3 min.
The hot air in the heat treatment equipment is not directly contacted with the mixture.
The pressure in the heat treatment equipment is 0.8 MPa.
The processing temperature of the mixed material in the processing equipment is 450 ℃.
Example 3
A method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln comprises the following steps:
step one, preparing a fluorine decomposition curing agent: adding 48kg of neodymium iron boron waste, 64kg of vanadium-titanium-containing slag, 15kg of iron-doped titanium dioxide, 28kg of electrolytic manganese-containing waste slag, 24kg of blast furnace slag and 8kg of molten copper slag into a grinding machine, and grinding into 160-mesh powder; then adding the powder into 400kg of acid solution with the molar concentration of 4mol/L, uniformly mixing, putting the material into a ball mill, carrying out ball milling for 5 hours, and filtering and separating to obtain activated slag powder; then adding the mixture into 2800kg of soda lime, and stirring and mixing uniformly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 180kg of fluorine-containing inorganic compound and 80kg of fluorine decomposition curing agent to obtain a mixed material, conveying the mixed material into drying equipment, drying at 100 ℃ to remove water, and conveying the dried mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides hot air at 600 ℃ in a cement kiln decomposition system into processing equipment to heat the mixed material, and the reaction time is 90 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
The preparation method of the iron-doped titanium dioxide comprises the following steps:
adding 30kg of titanium dioxide into 300kg of white oil, adding 5kg of compound with sulfydryl and silicon base, introducing nitrogen, stirring and reacting for 60min at 50 ℃, then adding 6.5kg of ferric acrylate, 0.25kg of 2-methoxy-6-vinyl phenylboronic acid and 3.6kg of sodium methoxide, slowly adding into a reaction kettle, heating to 62 ℃, stirring and reacting for 300min, filtering, and drying to obtain the iron-doped titanium dioxide.
The compound with sulfydryl and silicon base is selected from gamma-mercaptopropylmethyldiethoxysilane.
The acid solution is acetic acid solution.
The mixed materials are stirred once in a device for processing 5 min.
The hot air in the heat treatment equipment is not directly contacted with the mixture.
The pressure in the heat treatment equipment is 1.6 MPa.
The treatment temperature of the mixed material in the treatment equipment is 550 ℃.
Crushing waste residues containing fluorine inorganic compounds into 300-mesh powder, adding 1.0g of sample into 10g of pure water, stirring and mixing for 12h, and then measuring the cyanide content by using an ion selective electrode method for measuring water quality fluoride according to the national standard GB 7484-; 3.0g of the biomass was dried at 100 ℃ for 5 hours and then incinerated at 500 ℃ for 40 minutes, and the incineration loss was measured, and the larger the incineration loss, the larger the organic matter residual amount. The test results are shown in the following table:
| fluoride residual (mg/L) | Incineration loss (%) | |
| Example 1 | 0.17 | 0.08 |
| Example 2 | 0.12 | 0.04 |
| Example 3 | 0.10 | 0.02 |
Comparative example 1
A method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln comprises the following steps:
the method comprises the following steps: preparation of fluorine decomposition curing agent: adding 23kg of neodymium iron boron waste, 32kg of vanadium-titanium-containing slag, 5kg of iron-doped titanium dioxide, 18kg of electrolytic manganese-containing waste slag, 8kg of blast furnace slag and 2kg of molten copper slag into a grinding machine, and grinding into 80-mesh powder; then adding the powder into 300kg of acid solution with the molar concentration of 0.5mol/L, uniformly mixing, putting the material into a ball mill, carrying out ball milling for 2 hours, and filtering and separating to obtain activated slag powder; then adding the mixture into 1500kg of soda lime, and stirring and mixing the mixture evenly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 100kg of fluorine-containing inorganic compound and 30kg of fluorine decomposition curing agent to obtain a mixed material, conveying the mixed material into drying equipment, drying and dewatering at 80 ℃, and conveying the mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides hot air at 500 ℃ in a cement kiln decomposition system into processing equipment to heat the mixed material, and the reaction time is 30 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
The preparation method of the iron-doped titanium dioxide comprises the following steps:
adding 20kg of titanium dioxide into 200kg of white oil, adding 2kg of compound with sulfydryl and silicon base, introducing nitrogen, stirring and reacting at 30 ℃ for 30min, adding 3.5kg of ferric acrylate and 2.2kg of sodium methoxide, slowly adding into a reaction kettle, heating to 50 ℃, stirring and reacting for 100min, filtering, and drying to obtain the iron-doped titanium dioxide.
The compound with mercapto and silicon group is selected from gamma-mercapto propyl trimethoxy silane.
The acid solution is oxalic acid solution.
The mixed materials are stirred once in a device for processing 2 min.
The hot air in the heat treatment equipment is not directly contacted with the mixture.
The pressure in the heat treatment equipment is 0.2 MPa.
The processing temperature of the mixed material in the processing equipment is 350 ℃.
Comparative example 2
A method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln comprises the following steps:
step one, preparing a fluorine decomposition curing agent: adding 23kg of neodymium iron boron waste, 32kg of vanadium and titanium containing slag, 18kg of electrolytic manganese-containing waste slag, 8kg of blast furnace slag and 2kg of molten copper slag into a grinding machine, and grinding into 80-mesh powder; then adding the powder into 300kg of acid solution with the molar concentration of 0.5mol/L, uniformly mixing, putting the material into a ball mill, carrying out ball milling for 2 hours, and filtering and separating to obtain activated slag powder; then adding the mixture into 1500kg of soda lime, and stirring and mixing the mixture evenly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 100kg of fluorine-containing inorganic compound and 30kg of fluorine decomposition curing agent to obtain a mixed material, conveying the mixed material into drying equipment, drying and dewatering at 80 ℃, and conveying the mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides hot air at 500 ℃ in a cement kiln decomposition system into processing equipment to heat the mixed material, and the reaction time is 30 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
The preparation method of the iron-doped titanium dioxide comprises the following steps:
adding 20kg of titanium dioxide into 200kg of white oil, adding 2kg of compound with sulfydryl and silicon base, introducing nitrogen, stirring and reacting for 30min at 30 ℃, adding 0.12kg of 2-methoxy-6-vinyl phenylboronic acid and 2.2kg of sodium methoxide, slowly adding into a reaction kettle, heating to 50 ℃, stirring and reacting for 100min, filtering, and drying to obtain the iron-doped titanium dioxide.
The compound with mercapto and silicon group is selected from gamma-mercapto propyl trimethoxy silane.
The acid solution is oxalic acid solution.
The mixed materials are stirred once in a device for processing 2 min.
The hot air in the heat treatment equipment is not directly contacted with the mixture.
The pressure in the heat treatment equipment is 0.2 MPa.
The processing temperature of the mixed material in the processing equipment is 350 ℃.
Comparative example 3
A method for cooperatively treating fluorine-containing inorganic compounds by a cement kiln comprises the following steps:
step one, preparing a fluorine decomposition curing agent: adding 10kg of iron-doped titanium dioxide into 150kg of soda lime, and stirring and mixing uniformly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 100kg of fluorine-containing inorganic compound and 30kg of fluorine decomposition curing agent to obtain a mixed material, conveying the mixed material into drying equipment, drying and dewatering at 80 ℃, and conveying the mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides hot air at 500 ℃ in a cement kiln decomposition system into processing equipment to heat the mixed material, and the reaction time is 30 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
The mixed materials are stirred once in a device for processing 2 min.
The hot air in the heat treatment equipment is not directly contacted with the mixture.
The pressure in the heat treatment equipment is 0.2 MPa.
The processing temperature of the mixed material in the processing equipment is 350 ℃.
The results of the performance test of the fluorine-containing inorganic compound waste residue of the comparative example are shown in the following table:
| fluoride residual (mg/L) | Incineration loss (%) | |
| Comparative example 1 | 0.27 | 0.18 |
| Comparative example 2 | 0.48 | 0.81 |
| Comparative example 3 | 0.72 | 1.17 |
Claims (8)
1. A method for co-processing fluorine-containing inorganic compounds by a cement kiln is characterized by comprising the following steps:
step one, preparing a fluorine decomposition curing agent: according to the mass parts, 23-48 parts of neodymium iron boron waste, 32-64 parts of vanadium-titanium-containing slag, 5-15 parts of iron-doped titanium dioxide, 18-28 parts of electrolytic manganese-containing waste residue, 8-24 parts of blast furnace slag and 2-8 parts of molten copper slag are added into a grinding machine and ground into powder of 80-160 meshes; then adding the powder into 300-400 parts of acid solution with the molar concentration of 0.5-4mol/L, uniformly mixing, putting the material into a ball mill, carrying out ball milling for 2-5h, and filtering and separating to obtain activated slag powder; then adding the mixture into 1500-2800 parts of soda lime, and stirring and mixing uniformly to obtain the fluorine decomposition curing agent;
step two, cooperative treatment: uniformly mixing 100-180 parts of fluorine-containing inorganic compound and 30-80 parts of fluorine decomposition curing agent to obtain a mixed material, feeding the mixed material into drying equipment, drying and dewatering at 80-100 ℃, and then conveying the mixed material into treatment equipment, wherein the treatment equipment is provided with a ventilation pipe leading to a cement kiln; the ventilation pipe guides hot air at the temperature of 500-600 ℃ in a cement kiln decomposition system into the treatment equipment to heat the mixed material, and the reaction time is 30-90 min;
and step three, using the thermal decomposition material as a cement kiln raw material for secondary utilization as a resource.
2. The method for the co-treatment of fluorine-containing inorganic compounds in a cement kiln according to claim 1, wherein:
the preparation method of the iron-doped titanium dioxide comprises the following steps:
adding 20-30 parts of titanium dioxide into 300 parts of white oil 200-fold, adding 2-5 parts of a compound with sulfydryl and silicon base, introducing nitrogen, stirring and reacting at 30-50 ℃ for 30-60min, then adding 3.5-6.5 parts of ferric acrylate, 0.12-0.25 part of 2-methoxy-6-vinyl phenylboronic acid and 2.2-3.6 parts of sodium methoxide, slowly adding into a reaction kettle, heating to 50-62 ℃, stirring and reacting for 100-fold for 300min, filtering, and drying to obtain the iron-doped titanium dioxide.
3. The method for the co-treatment of fluorine-containing inorganic compounds in the cement kiln according to claim 2, wherein:
the compound with mercapto and silicon group is selected from gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropylmethyldiethoxysilane, mercaptomethyltrimethoxysilane and mercaptomethyltriethoxysilane.
4. The method for the co-treatment of fluorine-containing inorganic compounds in the cement kiln according to claim 3, wherein:
the iron-doped titanium dioxide is subjected to surface treatment by adopting gamma-mercaptopropyltrimethoxysilane, and then undergoes Michael addition reaction with iron acrylate and 2-methoxy-6-vinylphenylboronic acid under the catalysis of sodium methoxide.
5. The method for the co-treatment of fluorine-containing inorganic compounds in a cement kiln according to claim 1, wherein: the acid solution is oxalic acid solution or formic acid solution or acetic acid solution.
6. The method for the co-treatment of fluorine-containing inorganic compounds in a cement kiln according to claim 1, wherein: the hot air in the treatment equipment is not directly contacted with the mixture.
7. The method for the co-treatment of fluorine-containing inorganic compounds in a cement kiln according to claim 1, wherein: the pressure in the treatment equipment is 0.2-1.6 MPa.
8. The method for the co-treatment of fluorine-containing inorganic compounds in a cement kiln according to claim 1, wherein: the treatment temperature of the mixed material in the treatment equipment is 350-550 ℃.
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| CN102531429B (en) * | 2012-01-16 | 2013-01-23 | 郑慧 | Method for synergetically treating fluorine-containing sludge in cement kiln |
| CN108772407B (en) * | 2018-06-22 | 2024-01-05 | 长沙中硅环保科技有限公司 | System and method for cooperatively disposing waste lithium ion batteries by cement kiln |
| CN109108049B (en) * | 2018-08-01 | 2021-06-18 | 湘潭大学 | Method and system for converting sodium-containing and fluorine-containing compounds in aluminum electrolysis hazardous waste residues |
| CN111689703B (en) * | 2020-06-15 | 2022-01-11 | 浙江红狮环保股份有限公司 | Method for cooperatively treating inorganic hazardous waste in cement kiln |
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