CN108547012B - Arsenic-containing waste treatment process, method for preparing inorganic fiber and method for recovering arsenic - Google Patents
Arsenic-containing waste treatment process, method for preparing inorganic fiber and method for recovering arsenic Download PDFInfo
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- CN108547012B CN108547012B CN201810242276.9A CN201810242276A CN108547012B CN 108547012 B CN108547012 B CN 108547012B CN 201810242276 A CN201810242276 A CN 201810242276A CN 108547012 B CN108547012 B CN 108547012B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the field of waste treatment, in particular to a treatment process of arsenic-containing waste, a method for preparing inorganic fiber and a method for recovering arsenic. A process for the treatment of arsenic-containing waste comprising the steps of: mixing the arsenic-containing waste with an inorganic raw material to obtain a first mixture, wherein the mass of the calcium compound and the silicon compound accounts for 60-80% of the mass of the first mixture. The first mixture is heated at 1300-. And preparing the inorganic fiber by using the excess material obtained after heating. The method can not only recover arsenic, but also prepare fibers by utilizing excess materials after the arsenic is recovered, further improves the utilization rate of waste materials, and integrally reduces the production cost.
Description
Technical Field
The invention relates to the field of waste treatment, in particular to a treatment process of arsenic-containing waste, a method for preparing inorganic fiber and a method for recovering arsenic.
Background
Generally, arsenic and its compounds in arsenic-containing waste materials also include silicon substances, calcium substances, magnesium oxide and other substances, and the current domestic and foreign methods for treating arsenic-containing waste residues can be divided into 2 types: one is to use the pyrogenic process of oxidizing roasting, reducing roasting and vacuum roasting to make treatment, arsenic can be directly recovered in the form of white arsenic; the other method is to adopt wet processes such as acid leaching, alkali leaching or salt leaching and the like to separate arsenic from slag. Then further adopting a vulcanization method for treatment or other harmless treatment. The waste residue obtained by separating arsenic is generally buried, but the waste residue contains metal copper, lead and a small amount of metal arsenic, and the substances are extremely difficult to degrade and accumulate in soil, so that soil pollution is easily caused, and the waste residue is not favorable for the real recycling of arsenic-containing waste materials. Meanwhile, silicon substances and calcium substances in the waste residue after arsenic recovery are not well utilized, so that a new arsenic-containing waste material recovery process needs to be designed, and the recovery value of the arsenic-containing waste material is further improved.
Disclosure of Invention
The invention provides a treatment process of arsenic-containing waste, which not only can recover arsenic, but also can utilize the residual material after recovering arsenic to prepare fibers, thereby further improving the utilization rate of the waste and integrally reducing the production cost.
The invention also provides a method for preparing inorganic fiber, which can further expand the application of the arsenic-containing waste and further improve the economic value of the arsenic-containing waste by utilizing the arsenic-containing waste.
The present invention also provides a method for recovering arsenic, which can efficiently recover inorganic arsenic while reducing the cost of recovering arsenic as a whole.
The invention is realized by the following steps:
a process for treating arsenic-containing waste comprising the steps of:
mixing the arsenic-containing waste with an inorganic raw material to obtain a first mixture, wherein the mass of the calcium compound and the silicon compound accounts for 60-80% of the mass of the first mixture;
heating the first mixture at 1300-;
and preparing the inorganic fiber by using the excess material obtained after heating.
A method for preparing inorganic fibers, which comprises the treatment process of the arsenic-containing waste.
A method for recovering arsenic, which comprises the treatment process of the arsenic-containing waste.
The invention has the beneficial effects that: according to the invention, the inorganic raw material is added into the arsenic-containing waste, so that the content of calcium compounds and silicon compounds in the first mixture is increased, the content of fiber-forming substances in the first mixture is increased, and then after the arsenic-containing waste recovers arsenic, the preparation of fibers can be carried out, the arsenic-containing waste can be fully recycled, the recycling mode of the arsenic-containing waste is expanded, meanwhile, the recycling cost of the arsenic-containing waste is reduced as a whole, the variety of samples obtained by recycling the arsenic-containing waste is expanded, and greater economic benefits are created.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The treatment process of arsenic-containing waste, the method for preparing inorganic fibers, and the method for recovering arsenic according to the embodiments of the present invention will be specifically described below.
A process for treating arsenic-containing waste comprising the steps of:
s1, heating and melting;
first, the arsenic-containing waste is mixed with an inorganic raw material to obtain a first mixture, so that the mass of the calcium compound and the silicon compound in the first mixture accounts for 60-80% of the mass of the first mixture. The arsenic-containing waste contains a large amount of arsenic-containing substances, silicon-containing substances such as silicon and silicon dioxide, and calcium-containing substances such as calcium and calcium oxide, but the separate recovery of the substances remaining after arsenic recovery is difficult and costly, and the substances are easily wasted if discarded directly. Therefore, the inventors thought that the fibers can be prepared by using calcium silicon in the arsenic-containing waste, but the content of the fiber-forming substance such as the content of the silicon substance and the calcium substance in the arsenic-containing waste is not enough, and therefore, the inventors have conducted creative work to find that the quality of the calcium compound and the silicon compound is adjusted by adding the inorganic raw material according to the content of the silicon substance and the calcium substance in the arsenic-containing waste, the content of the fiber-forming substance in the first mixture is increased, and the subsequent fiber formation is facilitated. And the mass of the calcium compound and the silicon compound accounts for 60-80% of the mass of the first mixture, so that the formation of the inorganic fiber can be ensured, and the prepared inorganic fiber has good performance.
Further, the inorganic raw material may be high calcium stone, coal gangue, etc.
Meanwhile, the mass ratio of calcium to silicon in the first mixture is 1.2-1.7:1, and the calcium silicate can be ensured to form fibers with proper length and good quality in the range.
And then heating the first mixture at 1300-1700 ℃, wherein the first mixture can be fully melted, thereby facilitating the overflow of arsenic. In this temperature range the arsenic species becomes a vapor from which the inorganic arsenic can then be recovered. At the same time, harmful organic substances in the arsenic-containing waste are decomposed at the temperature to become gaseous nitrogen compounds and gaseous sulfur compounds, and the harmful substances can be removed through denitration and desulfurization, so that the arsenic-containing waste can be further purified.
Although the cost for recovering arsenic is increased to a certain extent by adopting a heating mode, a large amount of organic matters can be decomposed by high-temperature heating, the toxic and side effects of arsenic-containing waste materials are further reduced, meanwhile, the preparation of fibers can be ensured by supplementing inorganic raw materials and melting, the cost for treating the arsenic-containing waste materials is reduced on the whole, more various products are obtained, and the industrial and economic benefits are greater.
S2, recycling arsenic;
the temperature of the steam containing the arsenic substances is reduced to 400-500 ℃, and the subsequent dust removal effect can be ensured. And the waste heat of which the temperature is reduced from 1300-1700 ℃ to 400-500 ℃ is used for heating the steam in a boiler or subsequently heating the steam.
The steam containing arsenic substances is cooled and then subjected to primary dust removal, so that the subsequent approaching inorganic arsenic is prevented from being polluted by dust in the steam, high-temperature electrostatic dust removal is effectively adopted, the dust removal efficiency of the high-temperature electrostatic dust removal reaches 99%, the dust in the steam containing the arsenic substances can be removed, and the purity of the subsequent obtained crystallized inorganic arsenic is further ensured. Meanwhile, the treatment capacity is large each time, and a large amount of steam of arsenic-containing substances can be treated.
And then further cooling the steam containing the arsenic substances to ensure that the temperature of the steam containing the arsenic substances reaches 150-200 ℃, and then condensing and recovering to obtain inorganic arsenic to form solid crystals, thereby realizing the recovery of the arsenic substances.
The remaining steam contains nitrogen and sulfur, which easily cause air pollution, and thus secondary dust removal, denitration, and desulfurization processes are required before discharging the steam. Therefore, the steam after recovering the inorganic arsenic is subjected to secondary dust removal, denitration and desulfurization in sequence, meets the emission standard and can be discharged.
The denitration and desulfurization are carried out by adopting the process or method in the prior art, and the detailed description is not given in the invention.
However, when the inorganic arsenic is recovered, the temperature of the steam is reduced to 150-.
In order to reduce the cost for recovering or preparing arsenic, the steam is heated by utilizing the waste heat in the steam cooling and condensation recovery processes to heat the steam after recovering the inorganic arsenic, and the temperature of the steam after heating is 350-400 ℃.
By adopting the method, arsenic substances in the arsenic-containing waste can be effectively recovered, and simultaneously, the cleanliness of the discharged gas is ensured and air pollution is prevented.
S3, preparing inorganic fibers;
the inorganic fiber is prepared by utilizing the excess material obtained by mixing, heating and melting the arsenic-containing waste and the inorganic raw material. The heated excess material contains substances capable of forming fibers, and the proportion of each substance is proper, so that the fiber forming effect is ensured.
Specifically, the remainder in the molten state after heating is firstly centrifuged, so that the liquid becomes agglomerated flocculent fibers, and simultaneously, the residual metal in the molten state of the raw material is solidified in the fibers to be in a stable glass state, and the metal content in the fibers also meets the standard.
However, in the fiber-forming process using the above method, there is a possibility that impurities such as dust or glass shot remain in the agglomerated fibers, and thus, it is necessary to remove these solid impurities. Specifically, deslagging is carried out, wherein deslagging is carried out by carrying out negative pressure adsorption on agglomerated flocculent fibers obtained after centrifugation. The fibre of reunion is blown away, and simultaneously, lighter fibre is adsorbed on netted conveyer belt, and heavier impurity then realizes preliminary slagging-off, guarantees fibrous purity through the mesh of netted conveyer belt.
And (3) concentrating after deslagging, specifically, introducing the fiber subjected to deslagging into a modification circulating pool and stirring. The fiber is further dispersed by stirring in the modified circulating pool, and simultaneously, the glass slag mixed in the fiber and the short fiber are settled at the bottom of the modified circulating pool, so that the fiber is further purified, and the fiber forming quality is ensured.
Meanwhile, the modifying circulating pool contains a softening agent and a dispersing agent, the content of the softening agent is three thousandth to five thousandth of the mass of the water in the modifying circulating pool, and the content of the dispersing agent is not more than one thousandth of the mass of the water in the modifying circulating pool. The addition of the softening agent and the dispersing agent is more beneficial to the dispersion of the fibers into single fiber bundles, and is convenient for improving the performance of the fibers, preventing the fibers from being broken and ensuring the fiber forming quality.
After the fiber is dispersed and softened by the modification circulating tank, thick slurry on the upper layer of the modification circulating tank is pumped away, and short and thick fibers further fall back by utilizing centrifugal force after the thick slurry is pumped away, so that the fiber forming quality is further optimized. Specifically, by means of centrifugal force, the thick stock can be raised in rotation, and the short and thick fibers then fall back again.
The concentrated and re-centrifuged fibers have good flexibility and certain length, but the fibers are too long to be combed and are easy to break, so that the fibers with different lengths need to be cut to obtain fiber bundles with basically the same length.
Specifically, the pressure is applied to the concentrated fibers to cut the long fibers, and the magnitude of the applied pressure is controlled according to the length of the fibers to be broken as required.
And then, performing thickness separation on the cut fibers, and further obtaining the fibers with the same quality, thickness and length, and further optimizing the quality of the fibers.
Specifically, the thickness separation is carried out by placing the cut fibers in water for standing, and meanwhile, slowly introducing gas into the water to enable the water to vibrate slightly, so that the fibers can be more conveniently separated. The coarse and fine separation results in fibers substantially above 3 microns.
And (3) directly dehydrating and drying the separated fibers with the diameter of more than 3 micrometers to obtain fibers with good quality, modifying the residual fibers, introducing the fibers to be modified into a modification tank for reinforcement, wherein the addition amount of the modifier is 5-10% of the mass of the fibers to be modified, so that the modification effect is ensured, and dehydrating and drying the modified fibers with the diameter of more than 1mm to obtain the fibers with good quality.
The embodiment of the invention also provides a method for preparing inorganic fibers, which comprises the treatment process of the arsenic-containing waste.
The embodiment of the invention also provides a method for recovering arsenic, which comprises the treatment process of the arsenic-containing waste.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a treatment process of arsenic-containing waste, which comprises the following steps:
s1, heating and melting;
mixing the arsenic-containing waste material and an inorganic raw material to obtain a first mixture, wherein the mass of calcium compounds and silicon compounds in the first mixture accounts for 60-80% of the mass of the first mixture, namely the content of calcium and silicon is 60-80%, and the mass ratio of calcium to silicon in the first mixture is 1.2-1.7:1, namely the ratio of calcium to silicon is 1.2-1.7: 1. Wherein the inorganic material may be high calcium stone, coal gangue, etc.
And then heating the first mixture at 1300-1700 ℃.
S2, recycling arsenic;
the temperature of the steam containing arsenic substances is reduced to 400-.
And then further cooling the steam containing the arsenic substances to ensure that the temperature of the steam containing the arsenic substances reaches 150-.
And then carrying out secondary dedusting, heating, denitration and desulfurization treatment on the steam in sequence. The temperature rise is to utilize the waste heat in the steam cooling and condensation recovery processes to raise the temperature of the steam after the inorganic arsenic is recovered, and the temperature of the steam after the temperature rise is 350-400 ℃.
S3, preparing inorganic fibers;
the excess material in the molten state after heating is firstly centrifuged, and then the agglomerated flocculent fibers obtained after centrifugation are absorbed under negative pressure.
And introducing the fiber subjected to deslagging into a modification circulating pool and stirring. The modifying circulation pool contains a softening agent and a dispersing agent, the content of the softening agent is three thousandth to five thousandth of the mass of the modifying circulation pool water, and the content of the dispersing agent is not more than one thousandth of the mass of the modifying circulation pool water.
Then the thick slurry on the upper layer of the modification circulating pool is pumped away, and meanwhile, the short and thick fibers further fall back by utilizing centrifugal force.
Pressure is applied to the concentrated fibers, which in turn causes the long fibers to be cut.
And (3) standing the cut fibers in water, and meanwhile, slowly introducing gas into the water to perform thickness separation, wherein the particle size of the separated fibers is basically more than 3 microns.
And finally, directly dehydrating and drying to obtain the fiber.
The present example also provides a method for preparing inorganic fibers, which includes the treatment process of arsenic-containing waste material described above.
The embodiment also provides a method for recovering arsenic, which comprises the treatment process of the arsenic-containing waste material.
Examples 2 to 5
Examples 2-5 were substantially identical to the operation of example 1, except that the operating conditions of examples 2-5 were varied, specifically, the operating conditions are as shown in Table 1.
TABLE 1 operating conditions for examples 2-5
In addition, in the embodiment 5, the limit is also introduced into the modification tank, the addition amount of the modifier is 5-10% of the mass of the fiber to be modified, and dehydration and drying are carried out after modification.
Examples of the experiments
The recovery rate and purity of arsenic prepared in examples 1-5 of the present invention were measured, and the results are shown in Table 2.
TABLE 2 results of arsenic detection
As can be seen from Table 2, the arsenic recovered by the method provided by the embodiment of the invention has high recovery rate and high purity, which indicates that the arsenic has high recovery efficiency and generates greater economic benefit.
The inorganic fibers prepared in example 1 of the present invention were tested, and the results are shown in Table 3.
Table 3 inorganic fiber test results
As can be seen from Table 3, the fiber prepared by the embodiment of the invention has high fire-proof grade and good corrosion resistance, and can be used as an industrial fire-proof material.
In summary, according to the invention, the inorganic raw material is added to the arsenic-containing waste material, so that the content of the calcium compound and the silicon compound in the first mixture is increased, the content of the fiber-forming substance in the first mixture is increased, the preparation of the fiber can be performed after the arsenic-containing waste material recovers arsenic, the arsenic-containing waste material can be fully recycled, the recovery mode of the arsenic-containing waste material is expanded, the cost for recovering the arsenic-containing waste material is reduced as a whole, the variety of the sample obtained by recovering the arsenic-containing waste material is expanded, and a greater economic benefit is created.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 (6)
1. A process for the treatment of arsenic-containing waste, comprising the steps of:
mixing the arsenic-containing waste with an inorganic raw material to obtain a first mixture, wherein the mass ratio of calcium to silicon in the first mixture is 1.2-1.7:1, and the mass of the calcium compound and the silicon compound accounts for 60-80% of the mass of the first mixture;
heating the first mixture at 1300-;
preparing inorganic fibers by using the excess materials obtained after heating;
the inorganic fiber is obtained by centrifuging the residual material in a molten state after heating, and then sequentially performing deslagging, concentration, cutting and thickness separation; the step of deslagging is to carry out negative pressure adsorption on the agglomerated flocculent fibers obtained after centrifugation;
the inorganic arsenic is recovered by cooling the steam, performing first dust removal, and then condensing and recovering the inorganic arsenic;
the steam after the inorganic arsenic is recovered is discharged after second dust removal, denitration and desulfurization are sequentially carried out;
before denitration, the steam after the inorganic arsenic is recovered is heated by utilizing the steam cooling and the waste heat in the condensation recovery process, and the temperature of the steam after the heating is 350-400 ℃.
2. The process for the treatment of arsenic-containing waste material as claimed in claim 1, wherein the first dust removal is high temperature electrostatic dust removal.
3. The process of claim 1, wherein the concentrating step comprises introducing the deslagged fibers into a modified circulation tank and stirring the fibers.
4. The treatment process of arsenic-containing waste material as claimed in claim 3, wherein the modifying circulation tank contains softener and dispersant, the content of said softener is three per thousand to five per thousand of the quality of the water in the modifying circulation tank, and the content of dispersant is not more than one per thousand of the quality of the water in the modifying circulation tank.
5. A method for producing inorganic fibers, characterized in that it comprises a process for the treatment of arsenic-containing waste material according to claim 1.
6. A method for recovering arsenic, characterized in that it comprises a process for the treatment of arsenic-containing waste material according to claim 1.
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| CN101768885B (en) * | 2010-02-22 | 2013-05-01 | 厦门市特纤机械设备有限公司 | Manufacturing method of inorganic fiber paper pulp |
| CN102286665B (en) * | 2011-09-05 | 2012-10-31 | 耒阳市焱鑫有色金属有限公司 | Comprehensive recovery method for complicated materials containing arsenic and valuable metal slag dust |
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