CN111939745A - Method for preparing desulfurizer from carbide slag, efficiently desulfurizing and utilizing desulfurized gypsum - Google Patents
Method for preparing desulfurizer from carbide slag, efficiently desulfurizing and utilizing desulfurized gypsum Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/80—Semi-solid phase processes, i.e. by using slurries
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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
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
- C04B11/264—Gypsum from the desulfurisation of flue gases
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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- B01D2251/604—Hydroxides
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- B01D2258/0283—Flue gases
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Abstract
The invention discloses a method for preparing a desulfurizer by carbide slag, efficiently desulfurizing and utilizing desulfurized gypsum, which comprises the following steps: 1) the process for preparing the desulfurizer from the carbide slag comprises the following steps: separating the carbide slag by adopting a gravity field to obtain a fine particle desulfurizer and impurity particles, wherein the removed impurity particles are used for preparing a silicon iron product and a cement additive; 2) and (3) wet desulphurization process: adding water into the fine-particle desulfurizer, pulping to prepare desulfurizer slurry, and carrying out contact reaction on sulfur-containing flue gas and the desulfurizer slurry to obtain a desulfurized gypsum raw material; 3) the utilization process of the desulfurized gypsum raw material comprises the following steps: dehydrating and carrying out crystal transformation and deep processing on the desulfurized gypsum raw material to obtain a gypsum product. The invention develops the complete technology of recycling and high-efficiency desulfurization of the carbide slag and high-value utilization of the carbide slag-based desulfurized gypsum through the gravity field enhanced fractional separation of different types of carbide slag, and has the advantages of simple process, short flow and no secondary solid waste discharge.
Description
Technical Field
The invention belongs to the technical field of resource recycling, and particularly relates to a method for preparing a desulfurizer, desulfurized gypsum and a gypsum product by quickly separating carbide slag impurities by a dry/wet method.
Background
Carbide slag is a solid waste generated in the process of preparing acetylene by reacting carbide with water, and the emission of the carbide slag in the polyvinyl chloride (PVC) industry is about 1800 ten thousand tons every year. The carbide slag contains rich calcium resources and has great potential utilization value, and the utilization ways mainly comprise building material production, environmental management and common calcium chemical products. The traditional process is mainly applied to cement production and addition, and because of the demand of production reduction and energy conservation in recent years, the consumption of the carbide slag is gradually reduced, the overall utilization rate is less than 40 percent, and a large amount of land is occupied by stacking, and the serious environmental pollution problem is caused.
The energy structure of China is mainly coal, and the flue gas discharged by coal combustion contains a large amount of SO2And a large amount of primary limestone resources are consumed for flue gas desulfurization. The calcium hydroxide content in the carbide slag reaches 80-90%, and the carbide slag can be used as a desulfurizer after impurity removal, so that the pollution problem caused by sulfur dioxide can be greatly reduced, and the utilization efficiency of the carbide slag is improved. The Chinese patent application CN 104437023A discloses a method for producing a calcium hydroxide desulfurizer by using waste carbide slag, which comprises the steps of crushing, drying, blending, grinding, homogenizing and the like, and the desulfurizer is prepared. The Chinese patent application CN 102886201A discloses a method for preparing a desulfurizing agent for a thermal power plant by using carbide slag, which comprises the steps of crushing, removing impurities, calcining, cooling and sieving the carbide slag as a raw material to obtain the desulfurizing agent. Chinese patent application CN 102658007A discloses a method for producing a passivated calcium oxide desulfurizer by using carbide slag, which comprises the steps of filtering and screening ferrosilicon particles by using a vibrating screen, then carrying out plate-and-frame filter pressing, adding a passivator and a reinforcing agent, extruding, granulating, drying, roasting at high temperature and the like to prepare the desulfurizer. However, the above process is complicated, and requires operations such as crushing, drying or high-temperature roasting, the overall process is long, the required cost is high, and the purity of the product is often insufficient; in addition, in the process of using carbide slag as a desulfurizing agent, the quality control of the desulfurized gypsum is still insufficient, and the method for using the desulfurized gypsum still needs to be researched.
In conclusion, a simpler method is needed to be found for preparing the desulfurizer from the carbide slag, so that the carbide slag is convenient to separate, the production cost of the desulfurizer is lower, and the product purity is high.
Disclosure of Invention
The invention provides a method for preparing a desulfurizer by carbide slag aiming at the defects in the prior art, which prepares the desulfurizer by quickly separating carbide slag impurities by a dry method and a wet method, efficiently removes sulfur in sulfur-containing flue gas, and simultaneously realizes resource utilization of byproduct desulfurized gypsum so as to solve the problems in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a desulfurizer by using carbide slag, efficiently desulfurizing and utilizing desulfurized gypsum comprises the following steps:
1) the process for preparing the desulfurizer from the carbide slag comprises the following steps:
separating the carbide slag by adopting a gravity field to obtain a fine particle desulfurizer and impurity particles, wherein the removed impurity particles are used for preparing a silicon iron product and a cement additive;
2) and (3) wet desulphurization process:
adding water into the fine-particle desulfurizer, pulping to prepare desulfurizer slurry, and carrying out contact reaction on sulfur-containing flue gas and the desulfurizer slurry to obtain a desulfurized gypsum raw material;
3) the utilization process of the desulfurized gypsum raw material comprises the following steps:
dehydrating the desulfurized gypsum raw material, performing crystal transformation and deep processing to obtain a gypsum product.
Preferably, in the step 1), the carbide slag is generated in a dry and/or wet acetylene production process.
Preferably, the gravitational field separation includes, but is not limited to, single stage and multi-stage combined air separation and/or cyclonic flow.
Preferably, in the step 1), the mass content of the fine desulfurizing agent particles with the particle size of less than 106 μm is more than 90%, and the mass content of the dry calcium oxide is more than or equal to 72%.
Preferably, in the step 2), the mass ratio of the fine particle desulfurizing agent to the water is 1:1-1: 10.
Preferably, in the step 2), the sulfur-containing flue gas is in contact with the desulfurizer slurry for reaction, the sulfur content in the sulfur-containing flue gas before the reaction is 500-4500ppm, and the sulfur content in the sulfur-containing flue gas after the reaction is 0.5-35 ppm.
Preferably, in the step 2), the main phase of the desulfurized gypsum raw material is calcium sulfate dihydrate, and the mass fraction of calcium sulfite is less than 1%.
Preferably, in the step 2), the particle size of the desulfurized gypsum raw material is controlled within the range of 10 to 1000 microns.
Preferably, in the step 3), the crystal transformation method is calcination, steaming or hydrothermal, the crystal transformation temperature is 20-200 ℃, the crystal transformation reaction time is 10-400min, and the crystal form of the transformed gypsum comprises alpha-hemihydrate gypsum or beta-hemihydrate gypsum.
Preferably, in step 3), the gypsum product is one or more of building gypsum, high-strength gypsum powder, paper-faced gypsum board and fiber-reinforced gypsum board.
Specifically, the method for preparing the desulfurizer by quickly separating the impurities of the dry/wet carbide slag, efficiently desulfurizing and utilizing the desulfurized gypsum comprises the following steps:
1) the process for preparing the desulfurizer from the carbide slag comprises the following steps:
separating calcium oxide particles with different particle size ranges from the dry/wet carbide slag by a gravity field separation method, and synchronously removing impurity particles to obtain a fine particle desulfurizer product with the particle size smaller than a certain size; the mass content of the granules with the grain diameter of less than 106 mu m of the fine grain desulfurizer product is more than 90 percent, and the mass content of the dry-based calcium oxide of the product is more than or equal to 72 percent;
2) and (3) wet desulphurization process:
adding water into the carbide slag-based desulfurizer obtained in the step 1) and pulping to prepare desulfurized slurry, introducing sulfur-containing flue gas in industries such as energy, metallurgy and the like into a desulfurization reaction tower, carrying out contact reaction with the carbide slag desulfurizer slurry through a spraying system to realize effective removal of sulfur dioxide, and controlling the appearance, phase and particle size of calcium sulfate crystals to obtain desulfurized gypsum; adding water into the carbide slag-based desulfurizer, and stirring to prepare desulfurized slurry, wherein the mass ratio of the carbide slag to the water is 1:1-1: 10; the sulfur-containing range of the sulfur-containing flue gas in the desulfurization process is 500-4500ppm, and the sulfur-containing range of the sulfur-containing flue gas after desulfurization is 0.5-35 ppm; the main phase of the desulfurized gypsum is calcium sulfate dihydrate, and the mass fraction of the calcium sulfite is less than 1%; the particle size range of the desulfurized gypsum is controlled to be 10-1000 microns;
3) the utilization process of the desulfurized gypsum comprises the following steps:
dehydrating and separating the desulfurized gypsum obtained in the step 2), crystallizing to obtain gypsum with a required crystal form, and preparing to obtain a series of gypsum products by further deep processing methods such as fine grinding, water hardening and the like; the desulfurization gypsum crystal transformation method in the crystal transformation process comprises but is not limited to calcination, steaming, hydrothermal treatment and the like, the crystal transformation temperature is 20-200 ℃, the crystal transformation reaction time is 10-400min, and the crystal form of the transformed gypsum comprises alpha-hemihydrate gypsum or beta-hemihydrate gypsum;
the carbide slag in the invention can be produced by dry and wet acetylene production processes.
The gravity field separation method is mainly based on the difference of basic physical properties such as particle size, density and the like of mixed components, and comprises but is not limited to single-stage and multi-stage combined separation methods such as air separation, cyclone and the like; can be single-stage winnowing, single-stage cyclone, multi-stage winnowing, multi-stage cyclone, combination of multi-stage winnowing and cyclone and the like.
In the invention, the fineness of the powder obtained by the fine grinding method is 0.2mm, and the sieve residue of the square-hole sieve is less than 9.5%; the mass ratio of the gypsum to the water in the water hardening process is 1:0.3-1:0.7, and the longitudinal breaking load of the building material product after water hardening is not less than 400N.
The gypsum products of the present invention include, but are not limited to, building gypsum, high-strength gypsum powder, paper-surface gypsum board, fiber-reinforced gypsum board, etc.
The invention provides a method for preparing a desulfurizer by quickly separating carbide slag impurities by a dry method and a wet method, efficiently desulfurizing and utilizing desulfurized gypsum, which comprises the following steps: carrying out size fraction separation and impurity removal on the dry/wet carbide slag by a gravity field separation method to obtain a fine particle desulfurizer product with the particle size smaller than a certain size; the product is applied to the wet flue gas desulfurization process in the industries of energy, metallurgy and the like, and the crystal form, the morphology and the particle size of the desulfurized gypsum are regulated and controlled; after the desulfurization gypsum is dehydrated and separated, the high-value gypsum product is prepared by adopting methods such as crystal transformation, fine grinding or water hardening and the like.
The invention develops the complete technology of recycling and high-efficiency desulfurization of carbide slag and high-value utilization of carbide slag-based desulfurized gypsum by the gravity field enhanced fractional separation of different types of carbide slag; the method has the advantages of simple process, short flow, no secondary solid waste discharge, effective solving of the pollution problem of the carbide slag and good economic and social values.
The method mainly aims at the problems in the prior art, realizes the rapid separation of impurities by the gravity field separation of the carbide slag, and performs crystal form regulation and high-value utilization of the desulfurization gypsum on the basis, thereby realizing the large-scale consumption of the carbide slag and the resource utilization of the desulfurization gypsum.
Compared with the prior art, the invention has the following beneficial effects:
after the treatment of the invention, the desulfurization rate is as high as 99.5%, and the purity of the desulfurized gypsum produced by the invention is as high as more than 98.5%, and the desulfurized gypsum can be better applied to the aspects of preparing building gypsum, high-strength gypsum powder, paper-surface gypsum boards, fiber reinforced gypsum boards and the like.
Drawings
FIG. 1 is a flow chart of the method for preparing gypsum products from carbide slag.
Detailed Description
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. Unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features. The description is only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The invention is described in further detail below with reference to the figures and the detailed description.
Example 1:
dry-process carbide slag is used as a raw material, a desulfurizing agent is prepared in a winnowing mode, the mass proportion of particles with the particle size less than 105 mu m of a product is 93.15%, the mass content of dry-base calcium oxide is 72.87%, the mass ratio of the desulfurizing agent to water is 1:1, desulfurizing agent slurry is prepared, and flue gas SO at the inlet of a desulfurization system is2The concentration is 4500ppm, the temperature of the desulfurizing tower is 30 ℃, the oxygen content of the flue gas is 12 percent, the pH value of the circulating slurry is kept between 5.0 and 5.5, the Ca/S ratio is 1.05, and the tail gas SO of 24 hours is actually measured2The concentration is always lower than 35ppm, the mass fraction of calcium sulfite in the desulfurized gypsum is 0.073%, the particle size range is controlled to be 1000 microns, the hydrothermal crystal transformation temperature of the desulfurized gypsum is 120 ℃, the crystal transformation reaction time is 85min, the alpha-hemihydrate gypsum is prepared, and the high-strength gypsum powder with the sieve residue of a 0.2mm square-hole sieve of less than 8.3% is obtained after fine grinding.
Example 2:
wet carbide slag is used as raw material, and the desulfurizing agent is prepared in a cyclone mode, wherein the grain size of the product is less than 105The proportion of micron particles is 94.23 percent, the content of dry calcium oxide is 73.51 percent, the mass ratio of the desulfurizer to the water is 1:3.5, the desulfurization slurry is prepared, and the flue gas SO at the inlet of a desulfurization system2The concentration is 1700ppm, the temperature of the desulfurizing tower is 40 ℃, the oxygen content of the flue gas is 8 percent, the pH value of the circulating slurry is kept between 5.2 and 5.6, the Ca/S ratio is 1.03, and the tail gas SO of 24 hours is actually measured2The concentration is always lower than 17ppm, the mass fraction of calcium sulfite in the desulfurized gypsum is 0.34%, the particle size range is controlled to be 50-800 microns, the calcination crystal transformation temperature of the desulfurized gypsum is 200 ℃, the crystal transformation reaction time is 30min, the beta-hemihydrate gypsum is obtained by preparing, the gypsum and the water are hardened under the condition that the mass ratio of the gypsum to the water is 1:0.6, the gypsum plaster board is obtained by preparing, and the longitudinal breaking load is 450N.
Example 3:
using wet-process carbide slag as a raw material, preparing a desulfurizing agent in a rotational flow mode, wherein the proportion of particles with the particle size of less than 105 mu m of the product is 90.21 percent, the content of dry-base calcium oxide is 72.05 percent, preparing desulfurizing slurry according to the mass ratio of the desulfurizing agent to water of 1:10, and preparing flue gas SO at the inlet of a desulfurizing system2Concentration 500ppm, measured 24 hours of tail gas SO2The concentration is always lower than 0.5ppm, the mass fraction of calcium sulfite in the desulfurized gypsum is 0.068%, the particle size range is controlled within 10-670 microns, the steaming and crystal transformation temperature of the desulfurized gypsum is 125 ℃, the crystal transformation reaction time is 300min, the alpha-hemihydrate gypsum is prepared, the gypsum and the water are hardened under the condition that the mass ratio of the gypsum to the water is 1:0.4, meanwhile, 2.1% of fibers are added, the fiber reinforced gypsum board is prepared, and the longitudinal fracture load is 800N.
Example 4:
the method comprises the steps of taking dry-process carbide slag as a raw material, preparing a desulfurizing agent in a rotational flow mode, preparing desulfurizing slurry by taking the mass ratio of the desulfurizing agent to water as 1:3, wherein the particle proportion of the product with the particle size of less than 105 mu m is 97.83%, the content of dry-base calcium oxide is 74.32%, and the mass ratio of the desulfurizing agent to the water is2Concentration 3700ppm, 24 hours measured SO of tail gas2The concentration is always lower than 15ppm, the mass fraction of calcium sulfite in the desulfurized gypsum is 0.015 percent, the particle size range is controlled between 50 and 1000 microns, the calcining and crystal transformation temperature of the desulfurized gypsum is 160 ℃, the crystal transformation reaction time is 150min, the beta-hemihydrate gypsum is prepared, and the 0.2mm square is obtained after fine grindingThe screen allowance of the mesh screen is less than 9.0 percent of the building gypsum.
Example 5:
the dry-process carbide slag is used as a raw material, a desulfurizing agent is prepared in a rotational flow mode, the proportion of particles with the particle size of less than 105 mu m of the product is 96.72 percent, the content of dry-base calcium oxide is 74.87 percent, the mass ratio of the desulfurizing agent to water is 1:6, desulfurizing slurry is prepared, and the flue gas SO at the inlet of a desulfurizing system2The concentration is 1200ppm, and the actual measurement shows that the tail gas SO is 24 hours2The concentration is always lower than 7ppm, the mass fraction of calcium sulfite in the desulfurized gypsum is 0.53 percent, the particle size range is controlled to be 10-830 microns, the calcination crystal transformation temperature of the desulfurized gypsum is 180 ℃, the crystal transformation reaction time is 10min, the beta-hemihydrate gypsum is prepared, the gypsum and the water are hardened under the condition that the mass ratio of the gypsum to the water is 1:0.4, meanwhile, fibers with the mass ratio of 3.0 percent are added, the fiber reinforced gypsum board is prepared, and the longitudinal fracture load is 520N.
Example 6:
the dry-process carbide slag is used as a raw material, a desulfurizer is prepared in a rotational flow mode, the proportion of particles with the particle size of less than 105 mu m is 98.72 percent, the content of dry-base calcium oxide is 75.18 percent, desulfurization slurry is prepared according to the mass ratio of the desulfurizer to water of 1:4.5, and flue gas SO at the inlet of a desulfurization system2The concentration is 1500ppm, the temperature of the desulfurizing tower is 45 ℃, the oxygen content of the flue gas is 8 percent, the pH value of the circulating slurry is kept between 5.3 and 5.6, the Ca/S ratio is 1.04, and the tail gas SO of 24 hours is actually measured2The concentration is always lower than 19ppm, the mass fraction of calcium sulfite in the desulfurized gypsum is 0.10%, the particle size range is controlled to be 50-600 microns, the calcination crystal transformation temperature of the desulfurized gypsum is 20 ℃, the crystal transformation reaction time is 400min, the beta-hemihydrate gypsum is obtained by preparing, the gypsum and the water are hardened under the condition that the mass ratio of the gypsum to the water is 1:0.7, the gypsum plaster board is obtained by preparing, and the longitudinal breaking load is 400N.
The method can be realized by upper and lower limit values and interval values of intervals of process parameters (such as temperature, time and the like), and embodiments are not listed.
Conventional technical knowledge in the art can be used for the details which are not described in the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and are not limited. Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing a desulfurizer by using carbide slag, efficiently desulfurizing and utilizing desulfurized gypsum comprises the following steps:
1) the process for preparing the desulfurizer from the carbide slag comprises the following steps:
separating the carbide slag by adopting a gravity field to obtain a fine particle desulfurizer and impurity particles, wherein the removed impurity particles are used for preparing a silicon iron product and a cement additive;
2) and (3) wet desulphurization process:
adding water into the fine-particle desulfurizer, pulping to prepare desulfurizer slurry, and carrying out contact reaction on sulfur-containing flue gas and the desulfurizer slurry to complete desulfurization and obtain a byproduct desulfurized gypsum;
3) the utilization process of the desulfurized gypsum raw material comprises the following steps:
and dehydrating the desulfurized gypsum, performing crystal transformation and deep processing to obtain a gypsum product.
2. The method according to claim 1, characterized in that in step 1), the carbide slag is produced by a dry and/or wet acetylene production process.
3. The method according to claim 1, wherein in step 1) the gravitational field separation comprises, but is not limited to, single stage and multi-stage combined air separation and/or swirling.
4. The method as claimed in claim 1, wherein in step 1), the mass content of the fine desulfurizing agent is more than 90% and the mass content of the dry calcium oxide is more than or equal to 72%.
5. The method as claimed in claim 1, wherein in the step 2), the mass ratio of the fine particle desulfurizing agent to the water is 1:1-1: 10.
6. The method as claimed in claim 1, wherein in step 2), the sulfur-containing flue gas is contacted with the desulfurizing agent slurry for reaction, the sulfur content in the sulfur-containing flue gas before the reaction is 500-4500ppm, and the sulfur content in the sulfur-containing flue gas after the reaction is 0.5-35 ppm.
7. The method as claimed in claim 1, wherein in the step 2), the main phase of the desulfurized gypsum is calcium sulfate dihydrate, and the mass fraction of the calcium sulfite is less than 1%.
8. The method as claimed in claim 1, wherein the particle size of the desulfurized gypsum in step 2) is controlled to be in the range of 10 to 1000 μm.
9. The method as claimed in claim 1, wherein in the step 3), the crystal transformation method is calcination, steaming or hydrothermal, the crystal transformation temperature is 20-200 ℃, the crystal transformation reaction time is 10-400min, and the crystal form of the transformed gypsum comprises alpha-hemihydrate gypsum or beta-hemihydrate gypsum.
10. The method of claim 1, wherein in step 3), the gypsum product is one or more of building gypsum, high strength gypsum powder, paper-faced gypsum board, and fiber-reinforced gypsum board.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112850773A (en) * | 2021-02-01 | 2021-05-28 | 贵州中亚高科涂料有限公司 | High-efficiency production method of high-purity semi-water desulfurization paste |
| CN112916594A (en) * | 2021-05-10 | 2021-06-08 | 中国科学院过程工程研究所 | Anti-condensation method in dry-method carbide slag recycling process |
| CN113929328A (en) * | 2021-11-15 | 2022-01-14 | 华能沁北发电有限责任公司 | Method for promoting crystal growth of desulfurized gypsum by regulating and controlling carbide slag-based desulfurizer |
| CN114590809A (en) * | 2022-01-06 | 2022-06-07 | 北京科技大学 | Preparation of desulfurizer from cyanamide waste residue and carbide slag and recycling of CO2Method (2) |
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