CN110332552B - Resourceful treatment system and method for chlorine-sulfur-containing organic waste liquid - Google Patents
Resourceful treatment system and method for chlorine-sulfur-containing organic waste liquid Download PDFInfo
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- CN110332552B CN110332552B CN201910285258.3A CN201910285258A CN110332552B CN 110332552 B CN110332552 B CN 110332552B CN 201910285258 A CN201910285258 A CN 201910285258A CN 110332552 B CN110332552 B CN 110332552B
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/02—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment
- F23G5/027—Incineration of waste; Incinerator constructions; Details, accessories or control therefor with pretreatment pyrolising or gasifying stage
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/08—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating
- F23G5/14—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion
- F23G5/16—Incineration of waste; Incinerator constructions; Details, accessories or control therefor having supplementary heating including secondary combustion in a separate combustion chamber
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
- F23G5/46—Recuperation of heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
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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
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
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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
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
- F23J15/04—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material using washing fluids
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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
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/06—Arrangements of devices for treating smoke or fumes of coolers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2201/00—Pretreatment
- F23G2201/30—Pyrolysing
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/10—Combustion in two or more stages
- F23G2202/103—Combustion in two or more stages in separate chambers
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2202/00—Combustion
- F23G2202/60—Combustion in a catalytic combustion chamber
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2206/00—Waste heat recuperation
- F23G2206/20—Waste heat recuperation using the heat in association with another installation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G2209/00—Specific waste
- F23G2209/10—Liquid waste
- F23G2209/101—Waste liquor
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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
- F23J2215/00—Preventing emissions
- F23J2215/20—Sulfur; Compounds thereof
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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
- F23J2215/00—Preventing emissions
- F23J2215/30—Halogen; Compounds thereof
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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
- F23J2215/00—Preventing emissions
- F23J2215/30—Halogen; Compounds thereof
- F23J2215/301—Dioxins; Furans
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/30—Technologies for a more efficient combustion or heat usage
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Abstract
The invention discloses a resourceful treatment system for organic waste liquid containing chlorine and sulfur, which comprises an incinerator, a waste heat boiler, a ceramic fiber tube catalytic dedusting bin, a primary absorption tower, a secondary absorption tower and a tertiary absorption tower which are sequentially connected, wherein a primary combustion chamber and a secondary combustion chamber are arranged in the incinerator, a catalyst for catalyzing sulfur dioxide to be converted into sulfur trioxide is attached to a ceramic fiber tube of the ceramic fiber tube catalytic dedusting bin, a spray opening of the primary absorption tower is connected with a concentrated sulfuric acid spray device to absorb sulfur trioxide in tower body flue gas, a spray opening of the secondary absorption tower is connected with a chlorine salt solution spray device to absorb sulfur dioxide in tower body flue gas, and a spray opening of the tertiary absorption tower is connected with a spray device to absorb hydrogen chloride in tower body flue gas. The resource treatment system method of the organic waste liquid containing chlorine and sulfur can recover the heat of the flue gas generated by burning the organic waste liquid and recover the chlorine and sulfur, and meanwhile, the overall cost is low.
Description
Technical Field
The invention relates to the technical field of waste liquid recovery and treatment, in particular to a recycling treatment system and method for organic waste liquid containing chlorine and sulfur.
Background
The general existing treatment method for treating organic waste liquid containing no sulfur, phosphorus, chlorine and the like comprises the steps of pretreating the waste liquid, grinding the pretreated waste liquid and coal powder to prepare slurry, burning and decomposing the slurry, treating flue gas by a purification system, recovering heat by a waste heat boiler, and removing conventional harmful impurities contained in the flue gas by a flue gas treatment system by using the heat generated by thermal decomposition of the flue gas so as to meet the emission standard.
The waste organic waste liquid containing harmful substances such as sulfur, phosphorus, chlorine and the like is decomposed by adopting a mixed burning method or a combustion-supporting method, heat and other recovery treatment are generally not carried out due to the worry about the corrosion resistance problem of equipment, and the high removal cost is required for a large amount of sulfuric acid, hydrochloric acid and phosphoric acid precursors.
Disclosure of Invention
The invention mainly aims to provide a resource treatment system and method for organic waste liquid containing chlorine and sulfur, which aim to recover heat of flue gas generated by burning the organic waste liquid and recover the chlorine and sulfur and have low overall cost.
In order to achieve the purpose, the invention provides a recycling treatment system for organic waste liquid containing chlorine and sulfur, which comprises an incinerator, a waste heat boiler, a ceramic fiber tube catalytic dust removal bin, a primary absorption tower, a secondary absorption tower and a tertiary absorption tower which are sequentially connected, wherein,
the incinerator is provided with a primary combustion chamber and a secondary combustion chamber, a catalyst for catalyzing conversion of sulfur dioxide into sulfur trioxide is attached to a ceramic fiber pipe of a ceramic fiber pipe catalytic dust removal bin, a spray opening of a primary absorption tower is connected with a concentrated sulfuric acid spray device to absorb sulfur trioxide in tower body flue gas, a spray opening of a secondary absorption tower is connected with a chlorine salt solution spray device to absorb sulfur dioxide in tower body flue gas, and a spray opening of a tertiary absorption tower is connected with a spray device to absorb hydrogen chloride in tower body flue gas;
organic waste liquid carries out the flue gas that the postcombustion produced in incinerator, enters into exhaust-heat boiler and carries out the heat transfer in order to drop to 300 ~620 ℃ with the flue gas temperature, ceramic fiber pipe dust removal and turn into sulfur trioxide with sulfur dioxide among the ceramic fiber pipe catalysis dust removal storehouse, and sulfur trioxide is absorbed through primary absorption tower to the flue gas, and sulfur dioxide is absorbed to secondary absorption tower, and the flue gas is discharged after the cubic absorption tower absorbs hydrogen chloride.
Preferably, the organic waste liquid resource treatment system containing chlorine and sulfur further comprises a neutralization flue gas treatment chamber communicated with the exhaust port of the tertiary absorption tower, and a spraying port of the neutralization flue gas treatment chamber is connected with a spraying device for spraying alkali liquor or liquid ammonia so as to discharge the flue gas after neutralization treatment.
Preferably, the incinerator is provided with a primary tuyere and a secondary tuyere which are respectively communicated with the primary combustion chamber and the secondary combustion chamber, and a drying and preheating device for drying and preheating air introduced into the incinerator is installed on a pipeline communicated with the primary tuyere and the secondary tuyere.
Preferably, the tower tops of the primary absorption tower, the secondary absorption tower and the tertiary absorption tower are all provided with a demisting device.
Preferably, the waste liquid outlets of the primary absorption tower, the secondary absorption tower and the tertiary absorption tower are communicated with the spraying ports thereof through pipelines.
The invention further provides a resource treatment method of the organic waste liquid containing chlorine and sulfur, which comprises the following steps:
the organic waste liquid enters an incinerator for combustion, and the moisture content of combustion air for primary combustion and secondary combustion is controlled to be 0.1g/Nm3The temperature is controlled to be between 200 ℃ and 300 ℃, the temperature in a secondary combustion chamber of the incinerator is between 900 ℃ and 1200 ℃, and the residence time of flue gas in the secondary combustion chamber is controlled to be 2 seconds to 4 seconds so as to ensure that the gasified gas of the organic waste liquid is fully thermally cracked;
flue gas generated after the organic waste liquid is incinerated enters a waste heat boiler through an exhaust port of the incinerator for heat exchange so as to utilize heat, and the temperature of the exhaust port of the waste heat boiler is controlled to be 300-620 ℃;
the flue gas after heat exchange of the waste heat boiler enters a ceramic fiber tube catalytic dust removal bin for conversion and dust removal, and sulfur dioxide in the flue gas is converted into sulfur trioxide under the action of a catalyst on the ceramic fiber tube and then enters a primary absorption tower;
reacting sulfur trioxide in the flue gas with concentrated sulfuric acid sprayed in the primary absorption tower, and then feeding the reaction product into a secondary absorption tower;
reacting sulfur dioxide in the flue gas with a chlorine salt solution sprayed in the secondary absorption tower, and then feeding the reaction product into a tertiary absorption tower;
and (4) reacting sulfur dioxide in the flue gas with spray water in the tertiary absorption tower, and then discharging tail gas.
Preferably, after the flue gas is treated by the tertiary absorption tower, the flue gas is also subjected to neutralization treatment by the neutralized flue gas treatment chamber so as to absorb acid gases in the flue gas.
Preferably, the temperature of the flue gas entering the primary absorption tower is reduced to below 250 ℃ by exchanging heat with dried air entering the furnace so as to avoid the generation of dioxin.
Preferably, the oxygen concentration in the flue gas at the outlet of the incinerator is controlled to be between 6 and 11 percent.
Preferably, the blast volume of the primary tuyeres and the secondary tuyeres in the incinerator is in the range of 1: 3-3: 5, so that the flue gas is uniformly mixed to ensure that the secondary combustion is fully combusted.
The organic waste liquid recycling treatment device provided by the invention has the advantages that through reasonable arrangement of all devices, on one hand, heat generated by burning the organic waste liquid is recycled, on the other hand, corrosion of waste gas to the devices is reduced, and simultaneously, acid gas generated by burning can be made into sulfuric acid, phosphoric acid, hydrochloric acid or salts thereof, so that the purposes of separation and recycling are achieved, and meanwhile, the treatment method is low in recycling cost. Meanwhile, the organic waste liquid recycling treatment device also has the advantages of simple structure, easy realization and reliable work.
Drawings
FIG. 1 is a schematic structural diagram of a recycling treatment system for organic waste liquid containing chlorine and sulfur;
FIG. 2 is a schematic flow chart of the resource treatment method of the organic waste liquid containing chlorine and sulfur.
In the figure, 10-incinerator, 20-exhaust-heat boiler, 30-ceramic fiber pipe catalytic dedusting bin, 40-primary absorption tower, 50-secondary absorption tower, 60-tertiary absorption tower, 70-neutralized flue gas treatment chamber and 80-circulating pump.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that in the description of the present invention, the terms "lateral", "longitudinal", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Referring to fig. 1 and 2, in the preferred embodiment, a recycling treatment system for organic waste liquid containing chlorine and sulfur comprises an incinerator 10, a waste heat boiler 20, a ceramic fiber tube catalytic dust removal bin 30, a primary absorption tower 40, a secondary absorption tower 50 and a tertiary absorption tower 60, which are connected in sequence, wherein,
a primary combustion chamber and a secondary combustion chamber are arranged in the incinerator 10, a catalyst for catalyzing conversion of sulfur dioxide into sulfur trioxide is attached to a ceramic fiber pipe of the ceramic fiber pipe catalytic dust removal bin 30, a spray opening of the primary absorption tower 40 is connected with a concentrated sulfuric acid spray device to absorb sulfur trioxide in tower body flue gas, a spray opening of the secondary absorption tower 50 is connected with a chlorine salt solution spray device to absorb sulfur dioxide in tower body flue gas, and a spray opening of the tertiary absorption tower 60 is connected with a spray device (pure water is used as an absorbent) to absorb hydrogen chloride in tower body flue gas;
the flue gas generated by secondary combustion of the organic waste liquid in the incinerator 10 enters the waste heat boiler 20 for heat exchange to reduce the temperature of the flue gas to 300-620 ℃, the ceramic fiber tubes in the ceramic fiber tube catalytic dust removal bin 30 remove dust from the flue gas and convert sulfur dioxide into sulfur trioxide, the flue gas passes through the primary absorption tower 40 to absorb sulfur trioxide to produce sulfuric acid, the secondary absorption tower 50 absorbs sulfur dioxide to produce sulfate, and the tertiary absorption tower 60 absorbs hydrogen chloride to produce hydrochloric acid and then discharges the flue gas.
The incinerator 10 is designed to meet both the requirement of corrosion protection and the requirement of gasification and secondary complete combustion of the waste liquid. By arranging the waste heat boiler 20, partial heat exchange and steam supply requirements can be met in the boiler, meanwhile, the waste heat boiler 20 can control the temperature of the outlet air to be in the temperature required by the rear section, and the generated steam is supplied for other production or other purposes of a company. The ceramic fiber pipe is made of ceramic fine fiber filaments by proper process into semi-closed pipe, one end of the pipe is closed, the other end of the pipe is provided with a vent hole sealed by a flange, and the vent hole is separated from the flange by a partitionThe tube wall of the ceramic fiber tube has a certain thickness, the waste gas passes through the tube wall of the ceramic fiber tube, and the dust in the waste gas is blocked on the outer layer of the tube wall. Catalyst (vanadium as main component, and other promoter added for reaction to 2SO2+O2=2SO3) The dust-free waste gas passes through the wall of a ceramic fiber pipe with a certain thickness and has enough contact time with the ceramic fiber impregnated with the catalyst, and harmful substances which are not easy to treat are converted into oxides which are relatively easy to treat under the guarantee of a certain temperature. The converted waste gas reaches the gas collecting bin through a flange hole of the ceramic fiber pipe, and enters the next working section after being concentrated. This application creatively is used for sulfur dioxide with ceramic fiber tube to turn into sulfur trioxide, turns into the gas of relatively easy absorption processing with the harmful gas that is difficult to handle, still reaches the purpose of dust removal simultaneously, not only make full use of the waste heat that the waste liquid schizolysis produced, simplified the process flow moreover, also reduced required equipment quantity, owing to in high temperature operation, also reduced the maintenance cost of equipment corrosion simultaneously.
Further, the organic waste liquid recycling treatment system containing chlorine and sulfur also comprises a neutralization flue gas treatment chamber 70 communicated with the exhaust port of the tertiary absorption tower 60, and a spraying port of the neutralization flue gas treatment chamber 70 is connected with a spraying device for spraying alkali liquor or liquid ammonia so as to discharge the flue gas after neutralization treatment. The waste water from the neutralized flue gas treatment chamber 70 can be used to produce salts, such as sodium sulfite. All wastes reach the discharge standard in general.
In this embodiment, the incinerator 10 is provided with a primary tuyere and a secondary tuyere which are respectively communicated with the primary combustion chamber and the secondary combustion chamber, and a drying and preheating device for drying and preheating the air introduced into the incinerator is installed on a pipe communicated with the primary tuyere and the secondary tuyere. Through carrying out dehydration in advance to the air of advancing the stove, reduced the moisture content of the air of advancing the stove to advance stove gas temperature through suitable heat transfer and improve before advancing the stove, in order to do benefit to the quick improvement of stove burning temperature. The process is beneficial to improving the heat utilization rate and reducing the corrosion to equipment.
Further, the top of the primary absorption tower 40, the secondary absorption tower 50 and the tertiary absorption tower 60 are all provided with a demisting device. The tower top of the primary absorption tower 40 is provided with a demisting facility, so that the basic separation of chloride, sulfide and phosphide can be achieved. The top of the secondary absorption tower 50 is provided with a demisting facility, so that on one hand, the aim of further purifying the hydrogen chloride gas is achieved, and on the other hand, the loss of the hydrogen chloride is reduced as much as possible.
Further, the waste liquid outlets of the primary absorption tower 40, the secondary absorption tower 50 and the tertiary absorption tower 60 are communicated with the spray openings thereof through pipelines (via a circulating pump 80), so that the sprayed absorbent is recycled.
The working process of the chlorine-sulfur-containing organic waste liquid recycling treatment device is as follows:
the organic waste liquid enters an incinerator 10 for combustion, and the moisture content of combustion air for primary combustion and secondary combustion is controlled to be 0.1g/Nm3The temperature of combustion air is controlled to be 200-300 ℃ (the dried air is sent into the incinerator 10 in two parts, and a small part of the dried air enters the primary combustion chamber at the lower part of the incinerator 10 to ensure the temperature required by fuel gasification, but the total oxygen is controlled to ensure that the generated fuel gas is not oxidized greatly, the air of the second part, namely the combustion-supporting gas entering the secondary combustion chamber, is required to ensure excessive quantity), the temperature in the secondary combustion chamber of the incinerator 10 is 900-1200 ℃, and the retention time of the flue gas in the secondary combustion chamber is controlled to be 2-4 seconds to ensure that the gasified gas of the organic waste liquid is cracked sufficiently;
flue gas generated after the organic waste liquid is incinerated enters the waste heat boiler 20 through an exhaust port of the incinerator 10 to exchange heat so as to utilize heat (on one hand, corrosion of equipment is reduced, on the other hand, heat of the flue gas is recovered), and the temperature of the exhaust port of the waste heat boiler 20 is controlled to be 300-620 ℃;
the flue gas after heat exchange by the exhaust-heat boiler 20 enters the ceramic fiber tube catalytic dust removal bin 30 for conversion and dust removal, and sulfur dioxide in the flue gas is converted into sulfur trioxide under the action of a catalyst on the ceramic fiber tube and then enters the primary absorption tower 40;
reacting sulfur trioxide in the flue gas with concentrated sulfuric acid sprayed in the primary absorption tower 40, and then feeding the reaction product into a secondary absorption tower 50;
the sulfur dioxide in the flue gas reacts with the chlorine salt solution sprayed in the secondary absorption tower 50 and then enters the tertiary absorption tower 60;
and reacting sulfur dioxide in the flue gas with spray water in the tertiary absorption tower 60 to generate hydrochloric acid, and discharging tail gas.
By utilizing the high-temperature filtering function of the ceramic fiber tube, unburned substances (such as carbon particles) in the flue gas and fly ash with the catalytic function are filtered and removed at high temperature, so that the generation of dioxin can be greatly reduced.
The water content of the combustion air of the primary combustion and the secondary combustion is controlled to be 0.1g/Nm3The temperature is controlled between 200 ℃ and 300 ℃, namely, the air entering the furnace is dehydrated and dried in advance, so that the moisture content of the air entering the furnace is reduced, and the temperature of the gas entering the furnace is increased through proper heat exchange before entering the furnace, so that the combustion temperature in the furnace is increased quickly. The process is beneficial to improving the heat utilization rate and reducing the corrosion to equipment. The temperature in the secondary combustion chamber of the incinerator 10 is controlled to be 900-1200 ℃, and the residence time of the flue gas in the secondary combustion chamber is controlled to be 2-4 seconds, so that the purpose of fully decomposing the combustion gas is achieved.
In addition, the organic waste liquid recycling treatment device can also be applied to the treatment of the organic waste liquid of the chlorine phosphorus sulfur, and the difference is that the smoke product in the incinerator 10 contains phosphide, the phosphide is in the primary absorption tower 40, and the product in the primary absorption tower 40 also comprises H3PO3 （P2O5And H2Reaction of O to H3PO3) Thus, the products in the primary absorber 40 are oleum and phosphoric acid.
By controlling the temperature of the exhaust port of the waste heat boiler 20 to be 300-620 ℃, impurity removal and catalytic conversion are carried out through the ceramic fiber pipe at the temperature, namely, operation is ensured at a higher temperature which is above the dew point of harmful inorganic acid impurities, and corrosion to equipment can be reduced. In addition, the process that the temperature is fully reduced to remove impurities such as dust and the like by a common impurity removal means and then the impurities are heated to the higher temperature for catalytic impurity removal is avoided.
The organic waste liquid recycling treatment device provided by the invention has the advantages that through reasonable arrangement of all devices, on one hand, heat generated by burning the organic waste liquid is recycled, on the other hand, corrosion of waste gas to the devices is reduced, and simultaneously, acid gas generated by burning can be made into sulfuric acid, phosphoric acid, hydrochloric acid or salts thereof, so that the purposes of separation and recycling are achieved, and meanwhile, the treatment method is low in recycling cost. Meanwhile, the organic waste liquid recycling treatment device also has the advantages of simple structure, easy realization and reliable work.
The invention further provides a recycling treatment method of the organic waste liquid containing chlorine and sulfur.
In the preferred embodiment, a recycling treatment method for organic waste liquid containing chlorine and sulfur comprises the following steps:
step S10, the organic waste liquid enters the incinerator 10 for burning, and the moisture content of the combustion air for the primary burning and the secondary burning is controlled to be 0.1g/Nm3The temperature is controlled to be between 200 ℃ and 300 ℃, the temperature in a secondary combustion chamber of the incinerator 10 is between 900 ℃ and 1200 ℃, and the residence time of flue gas in the secondary combustion chamber is controlled to be 2 seconds to 4 seconds so as to ensure that the gasified gas of the organic waste liquid is fully thermally cracked;
step S20, enabling flue gas generated after the organic waste liquid is incinerated to enter the waste heat boiler 20 through an exhaust port of the incinerator 10 for heat exchange so as to utilize heat, and controlling the temperature of the exhaust port of the waste heat boiler 20 to be 300-620 ℃;
step S30, the flue gas after heat exchange by the exhaust-heat boiler 20 enters the ceramic fiber tube catalytic dust removal bin 30 for conversion and dust removal, and sulfur dioxide in the flue gas is converted into sulfur trioxide under the action of a catalyst on the ceramic fiber tube and then enters the primary absorption tower 40;
step S40, reacting sulfur trioxide in the flue gas with concentrated sulfuric acid sprayed in the primary absorption tower 40, and then entering the secondary absorption tower 50;
step S50, reacting sulfur dioxide in the flue gas with the chlorine salt solution sprayed in the secondary absorption tower 50, and then entering the tertiary absorption tower 60;
and step S60, reacting sulfur dioxide in the flue gas with spray water in the tertiary absorption tower 60, and then discharging the flue gas.
The organic waste liquid recycling method is also applicable to the organic waste liquid treatment of the phosphorus chloride and sulfur, and is characterized in that the smoke product in the incinerator 10 contains phosphide, the phosphide reacts with an absorbent in the primary absorption tower 40, and the product in the primary absorption tower 40 also comprises H3PO3 （P2O5And H2Reaction of O to H3PO3) Therefore, the products in the primary absorption tower 40 are fuming sulfuric acid and phosphoric acid, and the products in the primary absorption tower 40 are separated subsequently to realize recovery.
In step S10, the oxygen concentration in the flue gas at the outlet of the incinerator 10 is controlled to be 6-11%. In addition, the amount of blast of the primary and secondary tuyeres in the incinerator 10 is controlled to be 1: 3-3: 5, so that the flue gas is uniformly mixed to ensure that the secondary combustion is fully combusted. The dried air is sent into the incinerator 10 in two parts, and a small part enters the lower part of the incinerator 10 to ensure the temperature required by fuel gasification, but the total oxygen is controlled to ensure that the generated fuel gas is not oxidized in a large amount, and the air of the second part is required to ensure excess, so that the temperature of secondary combustion can be ensured to be 900-1200 ℃.
In step S40, the flue gas entering the primary absorption tower 40 is subjected to heat exchange with the dried air entering the furnace to reduce the temperature thereof to below 250 ℃ so as to avoid the generation of dioxin. The converted and dedusted gas exchanges heat with dried air entering the furnace to achieve the purposes of primary cooling and reasonable energy utilization, the high-temperature dust filtration and clean gas cooling can greatly eliminate the catalytic effect of fly dust on the synthesis of dioxin, and the aim of safely passing through a temperature window for re-synthesis of dioxin at the temperature of 250-500 ℃ is achieved; in the first absorption tower, the temperature is reduced by 93-98 percent of sulfuric acid to absorb SO in the first absorption tower3And oxides of phosphorus, and a demisting facility is arranged at the top of the tower, so that the basic separation of chloride, sulfur and phosphorus can be achieved.
In the primary absorption tower 40, the absorbent with appropriate moisture content is selected, so that the absorption efficiency of sulfur and phosphorus oxides is ensured, the concentration of the prepared acid is controlled, the escape and separation of other gases such as hydrogen chloride are ensured, and the escape of sulfur and phosphorus oxides which are already formed into acid and dissolved and adsorbed is prevented by further cooling and demisting before the separated gas escapes. The absorbent is sprayed into the primary absorption tower 40 through a corrosion-resistant acid circulating pump, the acid added with certain pure water is properly diluted after absorption and thickening, part of the diluted acid solution enters the primary absorption tower 40 through the corrosion-resistant pump circulating pump, the redundant part is taken out for assay, comprehensive utilization is carried out according to the quality, further purification and separation can be carried out to prepare high-quality phosphoric acid or phosphate without fluorine, and industrial sulfuric acid and powdered rock phosphate can be added to prepare agricultural phosphate fertilizer or feed phosphate and the like. The tower top is provided with a demisting facility, so that the basic separation of chloride, sulfur and phosphorus can be achieved. The waste gas such as hydrogen chloride from the primary absorption tower 40 enters the next section. The process design is different from the common separation process, mainly aims to simplify equipment and working procedures, simplify the anticorrosion requirement of the equipment and reduce the equipment investment.
The hydrogen chloride-containing waste gas escaping from the separation section of the primary absorption tower 40 contains a small amount of unconverted sulfur dioxide gas, if the mixed acid with poor quality is directly absorbed, and the standard emission of sulfur cannot be guaranteed due to the strong acidity of hydrochloric acid, so that a chloride solution with proper concentration is selected and added with a small amount of sulfur dioxide enhanced absorbent (in the secondary absorption tower 50, sulfur dioxide generates sulfite and is further oxidized into sulfate), the aim of further purifying the hydrogen chloride gas is achieved in the secondary absorption tower, the loss of hydrogen chloride is reduced as much as possible, and a proper demisting facility is installed at the top of the tower.
Purified water is adopted in the tertiary absorption tower 60 to absorb hydrogen chloride in the flue gas to obtain white hydrochloric acid meeting the market standard, a demisting facility is arranged at the top of the tower, the purified water used for absorption can be prepared by a reverse osmosis or ion exchange method, and the prepared water meets the relevant standard requirements. The exhaust gas from tertiary absorber 60 has substantially met the emission requirements.
Further, after the step S60, the flue gas is processed by the third absorption tower 60, and then is neutralized by the neutralized flue gas processing chamber 70 to absorb acid gases (including sulfur dioxide and hydrogen chloride) in the flue gas. The waste gas after absorbing the hydrogen chloride gas is neutralized by the flue gas treatment chamber 70 to be subjected to re-desulfurization, deacidification and other treatments, so that the standard emission standard requirement is met, and then the standard emission is carried out through a reasonable height.
The organic waste liquid containing chlorine and sulfur before entering the incinerator 10 is classified and analyzed, and is appropriately prepared based on the analysis result. Special attention is paid to the stability of the sulfur content in the mixed solution (control of SO in the gas phase)2The volume content is 1-5%), which not only ensures the stability of the sulfur dioxide content in the waste gas after combustion, but also is beneficial to the operation stability of subsequent working procedures, and is beneficial to effectively suppressing the generation of dioxin, and the existence of sulfur is beneficial to suppressing the dioxin.
The lower the CO concentration in the exhaust gas generated after the reaction in the incinerator 10, the more sufficient the combustion, and the CO concentration is preferably controlled to 60mg/m3The following. On the other hand, the synthesis of the dioxin precursor is controlled, the temperature of the secondary combustion chamber is controlled to reach 900-1200 ℃, and the residence time of the flue gas at a high temperature is controlled to reach 2-4 seconds. Meanwhile, the concentration of oxygen is controlled to be kept in a proper range, and the concentration of oxygen is controlled to be 6-11%. The time of the flue gas in the temperature range of 250-550 ℃ is shortened (or the condition of the flue gas passing through the temperature window is changed), the temperature of the flue gas is controlled at a proper temperature by the waste heat boiler 20, the subsequent process requirements are met, the temperature of the outlet gas is controlled at 500-550 ℃ and cannot exceed 550 ℃.
In addition, the content of sulfur, phosphorus and chlorine in the general waste liquid belongs to medium content, the content of sulfur, phosphorus and chlorine in the waste liquid cannot meet the conventional economic utilization content requirement, if the conventional economic content requirement of sulfur is more than 1.5%, the sulfur with the content of 1.0-1.5% is completely subjected to harmless treatment, the treatment cost is high, the stable operation and the full standard operation are not easy, and the secondary pollution is easy to cause. The treatment method converts sulfur as much as possible into sulfur trioxide capable of being absorbed and utilized at higher temperature through the special ceramic fiber tube, and meanwhile, the time for passing through the catalyst layer of the ceramic fiber tube is short, so that the temperature rise of the catalyst is controlled to be ultrahigh, the catalyst is prevented from losing efficacy, the purpose of recovering sulfur is achieved, and meanwhile, the recovery cost is low.
The method for recycling the organic waste liquid containing chlorine and sulfur has the following beneficial effects:
1. by adopting a proper absorbent, the generated harmful gas with higher content is cooled, absorbed and utilized by stages under the condition of ensuring the safe and stable operation of the equipment, and the harmful gas is separated to prepare acid or salt meeting relevant standards. And the residual trace harmful gas is treated by waste gas treatment methods such as ammonia addition and deacidification, so that the standard emission of the waste gas is ensured. In the process, part of the temperature reduction process (in the primary absorption tower 40) adopts furnace-entering dry and cold air for cooling and heat exchange, so that the temperature of the furnace-entering air is increased, and the gasification and combustion temperature is ensured to quickly meet corresponding requirements;
2. the organic waste liquid recycling method can enable waste liquid to be fully combusted, so that corrosion of waste gas to equipment is reduced, in addition, acid gas generated by burning the organic waste liquid is made into sulfuric acid, phosphoric acid, hydrochloric acid or salts thereof by reasonably arranging a plurality of processes and reasonably controlling each process parameter and adopting a sectional absorption method, so that the purposes of separation and recycling are achieved, and meanwhile, the recycling cost of the processing method is low;
3. the organic waste liquid recycling treatment method creatively uses the ceramic fiber tube to convert sulfur dioxide into sulfur trioxide, converts harmful gas which is not easy to treat into gas which is relatively easy to absorb and treat, and simultaneously achieves the aim of dust removal.
The above description is only for the preferred embodiment of the present invention and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or any other related technical fields, are intended to be covered by the scope of the present invention.
Claims (9)
1. A resourceful treatment system for organic waste liquid containing chlorine and sulfur is characterized by comprising an incinerator, a waste heat boiler, a ceramic fiber tube catalytic dedusting bin, a primary absorption tower, a secondary absorption tower and a tertiary absorption tower which are sequentially connected, wherein,
the incinerator is provided with a primary combustion chamber and a secondary combustion chamber, a catalyst for catalyzing conversion of sulfur dioxide into sulfur trioxide is attached to a ceramic fiber pipe of a ceramic fiber pipe catalytic dust removal bin, a spray opening of a primary absorption tower is connected with a concentrated sulfuric acid spray device to absorb sulfur trioxide in tower body flue gas, a spray opening of a secondary absorption tower is connected with a chlorine salt solution spray device to absorb sulfur dioxide in tower body flue gas, and a spray opening of a tertiary absorption tower is connected with a spray device to absorb hydrogen chloride in tower body flue gas;
flue gas generated by secondary combustion of organic waste liquid in an incinerator enters a waste heat boiler for heat exchange to reduce the temperature of the flue gas to 300-620 ℃, a ceramic fiber tube in a ceramic fiber tube catalytic dust removal bin removes dust from the flue gas and converts sulfur dioxide into sulfur trioxide, the flue gas absorbs the sulfur trioxide through a primary absorption tower, the sulfur dioxide is absorbed through a secondary absorption tower, and the flue gas is discharged after hydrogen chloride is absorbed through a tertiary absorption tower; purified water is adopted in the tertiary absorption tower to absorb hydrogen chloride in the flue gas, so that white hydrochloric acid meeting the market standard is obtained; and waste liquid outlets of the primary absorption tower, the secondary absorption tower and the tertiary absorption tower are communicated with respective spraying ports through pipelines and circulating pumps.
2. The chlorine-sulfur-containing organic waste liquid recycling treatment system as claimed in claim 1, further comprising a neutralized flue gas treatment chamber communicated with the exhaust port of the tertiary absorption tower, wherein the spraying port of the neutralized flue gas treatment chamber is connected with a spraying device for spraying alkali liquor or liquid ammonia so as to discharge the neutralized flue gas.
3. The organic waste liquid recycling system for chlorine-containing sulfur as claimed in claim 1, wherein said incinerator is provided with a primary tuyere and a secondary tuyere communicating with the primary combustion chamber and the secondary combustion chamber, respectively, and a drying and preheating device for drying and preheating the air introduced into the incinerator is installed on the pipe communicating with the primary tuyere and the secondary tuyere.
4. The recycling system for organic waste liquid containing chlorine and sulfur as claimed in claim 1, wherein the top of the primary absorption tower, the secondary absorption tower and the tertiary absorption tower are all provided with demisting devices.
5. A resource treatment method of organic waste liquid containing chlorine and sulfur is characterized by comprising the following steps:
the organic waste liquid enters an incinerator for combustion, and the moisture content of combustion air for primary combustion and secondary combustion is controlled to be 0.1g/Nm3The temperature is controlled to be between 200 ℃ and 300 ℃, the temperature in a secondary combustion chamber of the incinerator is between 900 ℃ and 1200 ℃, and the residence time of flue gas in the secondary combustion chamber is controlled to be 2 seconds to 4 seconds so as to ensure that the gasified gas of the organic waste liquid is fully thermally cracked;
flue gas generated after the organic waste liquid is incinerated enters a waste heat boiler through an exhaust port of the incinerator for heat exchange so as to utilize heat, and the temperature of the exhaust port of the waste heat boiler is controlled to be 300-620 ℃;
the flue gas after heat exchange of the waste heat boiler enters a ceramic fiber tube catalytic dust removal bin for conversion and dust removal, and sulfur dioxide in the flue gas is converted into sulfur trioxide under the action of a catalyst on the ceramic fiber tube and then enters a primary absorption tower;
reacting sulfur trioxide in the flue gas with concentrated sulfuric acid sprayed in the primary absorption tower, and then feeding the reaction product into a secondary absorption tower;
reacting sulfur dioxide in the flue gas with a chlorine salt solution sprayed in the secondary absorption tower, and then feeding the reaction product into a tertiary absorption tower;
reacting sulfur dioxide in the flue gas with spray water in the tertiary absorption tower, and then discharging tail gas; and waste liquid outlets of the primary absorption tower, the secondary absorption tower and the tertiary absorption tower are communicated with respective spraying ports through pipelines and circulating pumps.
6. The method as claimed in claim 5, wherein the flue gas is treated in the three absorption towers and then neutralized in the neutralized flue gas treatment chamber to absorb the acidic gases in the flue gas.
7. The method as claimed in claim 5, wherein the flue gas entering the primary absorption tower is subjected to heat exchange with the dried air entering the furnace to reduce the temperature to below 250 ℃ so as to avoid the generation of dioxin.
8. The method as claimed in claim 5, wherein the concentration of oxygen in the flue gas at the outlet of the incinerator is controlled to 6-11%.
9. The method for recycling organic waste liquid containing chlorine and sulfur according to claim 5, wherein the blast volume of the primary tuyere and the secondary tuyere in the incinerator is in the range of 1: 3-3: 5, so that the flue gas is uniformly mixed to ensure that the secondary combustion is fully combusted.
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