CN107746066B - Ammonium chloride preparation system and method for ash plasma melting treatment system - Google Patents
Ammonium chloride preparation system and method for ash plasma melting treatment system Download PDFInfo
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- C01—INORGANIC CHEMISTRY
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- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention provides an ammonium chloride preparation system and an ammonium chloride preparation method for an ash plasma melting treatment system. According to the invention, the problems of secondary hazardous waste generation, high energy consumption, complex equipment and the like of the existing system for absorbing the acid gas generated by the ash plasma melting treatment system can be solved.
Description
Technical Field
The invention relates to the field of waste incineration treatment, in particular to an ammonium chloride preparation system and an ammonium chloride preparation method for an ash plasma melting treatment system.
Background
Ash slag is the abbreviation of fly ash and bottom slag, wherein the fly ash is tiny particles discharged along with flue gas in the process that garbage or dangerous waste is not burned, contains substances such as heavy metal, dioxin and the like, and belongs to dangerous waste; the bottom slag is a burnout material generated in the incineration process of garbage or dangerous waste, contains heavy metals and also belongs to dangerous waste.
The fly ash generated by burning the household garbage and the fly ash and bottom slag generated by burning the dangerous waste belong to the category of the dangerous waste, and the current treatment mode aiming at the dangerous waste is mainly safe landfill and has higher cost. The fly ash and the bottom slag can be innocent treated, volume reduced and recycled through the plasma melting technology, and the plasma melting furnace adopting the plasma melting technology is a reactor which rapidly changes the fly ash and the bottom slag into a molten state through high temperature (the central area can reach 7000 ℃) generated by plasma electric arc, and is a mode and a device for innocent treatment and recycling of the fly ash and the bottom slag.
As the fly ash and the bottom slag usually contain more chlorine elements, the content is generally 4% -27%, in the process of plasma melting treatment of the ash slag, the chlorine elements are converted into hydrogen chloride to be discharged from the flue gas, and acid gas is required to be absorbed for reaching the discharge standard. In general, after the flue gas is subjected to waste heat recovery and temperature reduction, hydrogen chloride in the flue gas is absorbed by water by using a falling film absorber or other means to form a hydrochloric acid solution, and in order to improve the absorption efficiency of hydrochloric acid, equipment such as three-stage graphite absorption is generally used. In addition, in order to increase the concentration of hydrochloric acid, the temperature of absorbed water is usually reduced to about 4 ℃, and a set of cooling refrigeration equipment is required to be additionally arranged. The system for absorbing the acid gas has the problems of high energy consumption, complex equipment and the like.
Therefore, there is a need to provide a new system and method for acid gas absorption to solve the above problems.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an ammonium chloride preparation system for a plasma melting treatment system of ash residues, wherein the ammonium chloride preparation system comprises an ammonia water spray tower, a concentrator and a crystallizer purification system which are sequentially connected, and a waste heat recoverer in the plasma melting treatment system provides steam for the concentrator and the crystallizer.
In one example, flue gas discharged by a plasma melting furnace in the plasma melting treatment system is sequentially subjected to cooling treatment of the waste heat recoverer and dust removal treatment of the bag-type dust remover and then is sent to the ammonia water spray tower.
In one example, the ammonia spray tower contacts ammonia with the flue gas in a counter-current manner.
In one example, the concentration of the ammonia water is 20% -30%, and the ammonia water is circularly sprayed.
In one example, the ammonia spray tower is provided in multiple stages.
In one example, the concentration of the ammonium chloride solution produced by the aqueous ammonia spray tower is 15% -40%.
In one example, the ammonium chloride solution enters the concentrator for concentration treatment, and the generated ammonium chloride saturated solution enters the crystallizer for crystallization treatment to generate crude ammonium chloride, and the concentrator and the crystallizer are decompression evaporation equipment.
In one example, the ammonium chloride production system further comprises a purification system coupled to the crystallizer to purify the crude ammonium chloride.
In one example, a secondary combustion chamber is further arranged between the plasma melting furnace and the waste heat recoverer to supplement oxygen and heat to the flue gas discharged by the plasma melting furnace, so that the temperature of the flue gas exceeds 1200 ℃.
In one example, the temperature of the flue gas discharged from the ammonia water spray tower is 50-80 ℃, and the flue gas is further treated by a post-treatment system.
The invention also provides a preparation method of ammonium chloride for the ash plasma melting treatment system, which comprises the following steps:
the flue gas discharged by a plasma melting furnace in the plasma melting treatment system is sent into an ammonia water spray tower after being sequentially subjected to cooling treatment of a waste heat recoverer and dust removal treatment of a bag-type dust remover;
the ammonium chloride solution generated by the ammonia water spray tower enters a concentrator for concentration treatment;
and the saturated ammonium chloride solution generated by the concentrator enters a crystallizer for crystallization treatment to generate crude ammonium chloride.
In one example, the method further comprises the step of feeding the crude ammonium chloride to a purification system for purification.
In one example, the flue gas is cooled to 180-200 ℃ after exchanging heat with deionized water in the waste heat recoverer, and low-pressure steam is generated at the same time.
In one example, the low pressure steam is provided to the concentrator and the crystallizer.
According to the invention, the problems of secondary hazardous waste generation, high energy consumption, complex equipment and the like of the existing system for absorbing the acid gas generated by the ash plasma melting treatment system can be solved.
Drawings
The following drawings of the invention are included to provide a further understanding of the invention. The drawings illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention.
In the drawings:
FIG. 1 is a schematic process diagram of an ammonium chloride production system for an ash plasma melt processing system according to an exemplary embodiment of the present invention.
Detailed Description
In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art, that the present invention may be practiced without one or more of these specific details. In other instances, well-known features have not been described in order to avoid obscuring the invention.
In the following description, specific method steps and/or structures are set forth in order to provide a thorough understanding of the present invention. It will be apparent that the invention may be practiced without limitation to the specific details known to those skilled in the art. The following detailed description of the preferred embodiments of the invention, however, the invention is capable of other embodiments in addition to those detailed.
It is to be understood that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. In the drawings, the size and relative sizes of layers and regions may be exaggerated for clarity. Like reference numerals refer to like elements throughout.
It will be understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. The singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The existing system for absorbing the acid gas generated by the ash plasma melting treatment system is used, so that in order to avoid the strong corrosivity of hydrochloric acid, the equipment needs to be prepared by materials such as graphite and the like, and the equipment cost is high; however, the hydrochloric acid is absorbed by using water, and the dissolving capacity of the water to the hydrogen chloride gas is limited, so that an effective means for solving the problem is to increase the contact area and the contact time of the hydrochloric acid.
Since hydrochloric acid has certain volatility and the volatility increases with the increase of the concentration of the hydrochloric acid, since the dissolution process of the hydrochloric acid is an exothermic process, the volatilization intensity and the temperature are in a positive correlation relationship, in the actual operation process, water absorbed by the hydrochloric acid is cooling water, the temperature is usually about 4 ℃, and in order to reach the temperature, refrigeration equipment is usually required to be additionally arranged, so that the operation energy consumption is greatly increased.
Because other components such as dust, metal chloride, sulfide and the like in the flue gas are also absorbed by the falling film absorber, the grade of the collected hydrochloric acid solution is low, the purification process of the hydrochloric acid is complex and high in cost, for example, a ceramic membrane filter is usually used for filtering the dust, the operation and maintenance cost is high, and the process for purifying the metal chloride and the sulfide is more complex and expensive, so that a large amount of waste acid is generated by using the process generally, and new industrial hazardous waste is caused.
In order to solve the technical problems, the invention provides an ammonium chloride preparation system for an ash plasma melting treatment system, which can solve the problems of secondary hazardous wastes, high energy consumption, complex equipment and the like in the existing system for absorbing acid gas generated by the ash plasma melting treatment system.
As shown in FIG. 1, the ammonium chloride preparation system for ash plasma melting treatment system provided by the invention comprises: ammonia water spray column, concentrator, crystallizer and purification system.
The ash slag and additives such as sand generated in the incineration process of the garbage and the hazardous waste are uniformly mixed by a feeding device according to a certain proportion and then are sent into a plasma melting furnace. Ash and slag are stored in an ash and slag bin, an additive is stored in an additive bin, the ash and slag in the ash and slag bin are conveyed to an ash and slag metering device through a discharge valve for ash and slag weighing, the additive in the additive bin is conveyed to an additive metering device through the discharge valve and a screw conveyor for additive weighing, and the ash and slag metering device and the additive metering device are independently arranged. And simultaneously, working gas for generating reducing atmosphere is also sent into the plasma melting furnace from the top of the plasma melting furnace, and the working gas adopts nitrogen.
The plasma is generated between a continuously depleted graphite electrode at the top of the furnace and an electrode at the bottom of the furnace, typically nitrogen as the plasma process gas. The plasma melting furnace is operated under micro negative pressure, and the refractory materials in the furnace are cooled by water, so that the erosion of the molten glass liquid and the plasma to the refractory materials in the furnace is reduced to the maximum extent. The mixed material input by the feeding device is rapidly melted by the high-temperature arc of 5000-8000 ℃ generated by the plasma, the formed molten glass liquid has conductivity, and the generated resistance heat and the plasma maintain the temperature of the molten glass liquid in the furnace at 1450-1600 ℃.
The molten glass continuously overflows out of the plasma melting furnace from a glass slag outlet at the lower part of the furnace, and is cooled to obtain glass slag. The recovered metal is discharged out of the furnace through a metal slag outlet at the lower part of the plasma melting furnace, and the metal alloy is obtained after cooling. Dioxin in ash is almost completely destroyed by high-temperature plasma and ultraviolet rays generated by the high-temperature plasma as well as molten glass liquid. The flow of the flue gas generated by the plasma melting furnace is very low, and about 200Nm is generated per ton of ash3The temperature of the flue gas discharged from the upper part of the plasma furnace is between 900 ℃ and 1100 ℃, and the flue gas contains components such as hydrogen chloride and the like.
In order to remove dioxin, combustible gas and other components in the flue gas, the flue gas discharged from the upper part of the plasma melting furnace is sent to the lower part of a secondary combustion chamber for proper oxygen supplementation and heat supplementation, and CO, CH4 and the like in the flue gas are thoroughly oxidized at a high temperature of over 1200 ℃.
In order to avoid the regeneration of dioxin, the flue gas discharged from the top of the secondary combustion chamber is rapidly cooled to 180-200 ℃ after exchanging heat with deionized water in a waste heat recoverer, low-pressure steam is generated at the same time, in order to ensure that the temperature of the flue gas is above the dew point of hydrogen chloride and avoid acid corrosion, the temperature of the flue gas is ensured to be above 200 ℃, and the temperature is not too high, so that the high-temperature damage to a bag-type dust collector at the rear end is avoided.
And then, injecting activated carbon into a flue gas pipeline connected with the waste heat recoverer and the bag-type dust collector through an activated carbon injection device so as to absorb trace dioxin which is possibly formed in the flue gas again. All secondary fly ash (including non-fused fly ash carried by flue gas, volatilized salts, etc.) will be captured by the bag filter in the bag-type dust collector, which may typically account for 10% of the input ash, and in order to reduce the final disposal of the secondary fly ash, we need to precisely control the furnace pressure of the plasma melting furnace while re-fusing some of the secondary fly ash, which makes it possible to finally control the secondary fly ash to around 3% of the input ash (the specific values relate to the components of the input ash).
The flue gas becomes clean after being filtered by the bag-type dust collector, thereby being beneficial to the ammonium chloride preparation system for the ash plasma melting treatment system to prepare ammonium chloride. The flue gas firstly enters an ammonia water spray tower in the ammonium chloride preparation system, ammonia water is used for spraying the flue gas, a countercurrent mode is optimized to enhance the reaction effect of ammonia and hydrogen chloride in the flue gas, the ammonia water is optimized to be concentrated ammonia water with the concentration of 20-30% (weight percent) to circularly spray the ammonia water, and the ammonia water spray tower can be also arranged into multiple stages in order to improve the absorption efficiency. The hydrogen chloride reacts with the ammonia to form an ammonium chloride solution, which may have a concentration of between 15% and 40% (by weight) and may contain ammonium sulfate, metal chlorides, etc.
The formed ammonium chloride solution is concentrated and crystallized by using steam generated in a waste heat recoverer, and because the solubility of ammonium chloride is increased along with the increase of temperature and the ammonium chloride is easy to decompose at higher temperature, the concentration and crystallization are preferably carried out by a decompression evaporation device. And the formed ammonium chloride solution enters a concentrator for concentration treatment, and the generated ammonium chloride saturated solution enters a crystallizer for crystallization treatment to generate crude ammonium chloride.
The ammonium chloride solid generated by concentration and crystallization treatment may contain a small amount of impurities such as sodium chloride, ammonium sulfate and the like, and can be directly used in occasions with low concentration requirements, but if the ammonium chloride is applied with high purity requirements, the ammonium chloride needs to be purified, crude ammonium chloride is sent into a purification system for purification treatment, and the preferred purification means is generated by heating, decomposition and condensation. The refined ammonium chloride solid with the purity of more than 99 percent can be obtained by the ammonium chloride preparation system for the ash plasma melting treatment system.
The temperature of the flue gas discharged from the ammonia water spray tower is 50-80 ℃, and the flue gas is further treated by a post-treatment system. As an example, flue gas discharged from the upper part of an ammonia water spray tower enters the lower part of a wet scrubbing tower, and SO contained in the flue gas2And a small amount of unabsorbed hydrogen chloride gas is neutralized with NaOH solution. And finally, the dust-free and acid-free clean flue gas is heated by a steam heater and then is merged into a waste incineration main flue gas purification system by a draught fan for treatment and then is discharged. The steam heater heats the flue gas to a non-saturated temperature range, so that the flue gas does not generate white mist. The outdoor temperature in summer is higher, the humidity is little, and the concentration and the diffusion area of white fog are limited, can use steam heater according to the circumstances, controls steam heater's opening and closing through setting up steam heat exchanger bypass valve.
The ammonium chloride preparation system for the ash plasma melting treatment system provided by the invention has the following advantages:
(1) because the reaction of the ammonia water and the hydrogen chloride is complete reaction, compared with the method of dissolving and absorbing the hydrogen chloride in the flue gas by using water, the reaction efficiency is greatly improved, and complex and expensive equipment such as a three-stage falling film absorber is not required;
(2) the reaction of the ammonia water and the hydrogen chloride is complete at normal temperature, so that the temperature of the circulating ammonia water does not need to be reduced, refrigeration equipment does not need to be added, and the operation energy consumption is greatly reduced;
(3) the steam generated by the waste heat recoverer is used for concentrating and crystallizing the ammonium chloride, so that additional heat input is not increased, and the operation cost is reduced;
(4) the obtained crude ammonium chloride can be directly used as an industrial raw material, if purification is needed, the ammonium chloride can be purified by heating and other modes, the process is simple, the cost is low, and the condition that a large amount of secondary pollutants such as waste acid and the like are generated is avoided.
The invention also provides a preparation method of ammonium chloride for the ash plasma melting treatment system, which comprises the following steps:
(a) flue gas discharged by a plasma melting furnace in the plasma melting treatment system is sent into an ammonia water spray tower after being sequentially subjected to cooling treatment of a waste heat recoverer and dust removal treatment of a bag-type dust collector;
(b) the ammonium chloride solution generated by the ammonia water spray tower enters a concentrator for concentration treatment;
(c) the saturated ammonium chloride solution generated by the concentrator enters a crystallizer for crystallization treatment to generate crude ammonium chloride;
(d) and (4) sending the crude ammonium chloride into a purification system for purification treatment according to requirements.
The present invention has been illustrated by the above embodiments, but it should be understood that the above embodiments are for illustrative and descriptive purposes only and are not intended to limit the invention to the scope of the described embodiments. Furthermore, it will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that many variations and modifications may be made in accordance with the teachings of the present invention, which variations and modifications are within the scope of the present invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (14)
1. The ammonium chloride preparation system is characterized by comprising an ammonia water spray tower, a concentrator and a crystallizer purification system which are sequentially connected, wherein a waste heat recoverer in the plasma melting treatment system provides steam for the concentrator and the crystallizer, the concentrator and the crystallizer are decompression evaporation equipment, and the steam is used as a heat source of the concentrator and the crystallizer.
2. The ammonium chloride preparation system of claim 1, wherein flue gas discharged from a plasma melting furnace in the plasma melting treatment system is sent to the ammonia water spray tower after being subjected to temperature reduction treatment of the waste heat recoverer and dust removal treatment of a bag-type dust remover in sequence.
3. The system of claim 2, wherein the ammonia spray tower contacts the flue gas with ammonia in a counter-current manner.
4. The system for preparing ammonium chloride according to claim 3, wherein the concentration of the aqueous ammonia is 20 to 30% by weight, and the aqueous ammonia is circularly sprayed.
5. The ammonium chloride production system according to any one of claims 1 to 4, wherein the aqueous ammonia spray tower is provided in multiple stages.
6. The system of claim 1, wherein the concentration of the ammonium chloride solution produced by the aqueous ammonia spray tower is between 15% and 40% (by weight).
7. The ammonium chloride preparation system of claim 6, wherein the ammonium chloride solution enters the concentrator for concentration treatment, and the generated ammonium chloride saturated solution enters the crystallizer for crystallization treatment to generate crude ammonium chloride, and the concentrator and the crystallizer are pressure-reduction evaporation equipment.
8. The ammonium chloride production system of claim 7 further comprising a purification system coupled to the crystallizer to purify the crude ammonium chloride.
9. The ammonium chloride preparation system of claim 2, wherein a secondary combustion chamber is further arranged between the plasma melting furnace and the waste heat recoverer to supplement oxygen and heat to the flue gas discharged from the plasma melting furnace, so that the temperature of the flue gas exceeds 1200 ℃.
10. The ammonium chloride preparation system of claim 1, wherein the temperature of the flue gas discharged from the ammonia water spray tower is 50 ℃ to 80 ℃, and the flue gas is further treated by a post-treatment system.
11. A preparation method of ammonium chloride for an ash plasma melting treatment system is characterized by comprising the following steps:
the flue gas discharged by a plasma melting furnace in the plasma melting treatment system is sent into an ammonia water spray tower after being sequentially subjected to cooling treatment of a waste heat recoverer and dust removal treatment of a bag-type dust remover;
the ammonium chloride solution generated by the ammonia water spray tower enters a concentrator for concentration treatment;
the saturated ammonium chloride solution generated by the concentrator enters a crystallizer for crystallization treatment to generate crude ammonium chloride; the waste heat recoverer provides steam for the concentrator and the crystallizer.
12. The method of claim 11, further comprising the step of feeding the crude ammonium chloride to a purification system for purification.
13. The method for preparing ammonium chloride according to claim 11, wherein the flue gas is cooled to 180-200 ℃ after exchanging heat with deionized water in the waste heat recoverer, and low-pressure steam is generated at the same time.
14. The method of claim 13, wherein the low pressure steam is provided to the concentrator and the crystallizer.
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| CN109173649A (en) * | 2018-05-28 | 2019-01-11 | 柏美迪康环境科技（上海）股份有限公司 | A kind of coke oven exhaust gas processing method and system |
| CN109205643B (en) * | 2018-07-11 | 2023-12-19 | 连云港市福源德邦科技发展有限公司 | Dry ammonium chloride tail gas comprehensive utilization device and method in soda production process |
| WO2023222433A1 (en) | 2022-05-17 | 2023-11-23 | Basf Se | Process for preparing ammonium chloride |
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