CN113069875A - Treatment system and process suitable for waste gas of circulating ammonia water pool of coking plant - Google Patents

Treatment system and process suitable for waste gas of circulating ammonia water pool of coking plant Download PDF

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CN113069875A
CN113069875A CN202110349095.8A CN202110349095A CN113069875A CN 113069875 A CN113069875 A CN 113069875A CN 202110349095 A CN202110349095 A CN 202110349095A CN 113069875 A CN113069875 A CN 113069875A
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waste gas
ammonia
solution
stirring
slag
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CN113069875B (en
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裴振
杨丙衡
杨爽
李宝东
谢国威
方会斌
窦吉平
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Sinosteel Anshan Research Institute of Thermo Energy Co Ltd
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Sinosteel Anshan Research Institute of Thermo Energy Co Ltd
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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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1487—Removing organic compounds
    • 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
    • B01D53/14—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 by absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/14—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 by absorption
    • B01D53/18—Absorbing units; Liquid distributors therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/406—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)

Abstract

A treatment system and a treatment process suitable for waste gas of a circulating ammonia water tank of a coking plant comprise a waste gas collecting cover, a collecting main pipe, an ammonia absorber, a plug-flow folded plate absorption tank and an absorption liquid tank, wherein an exhaust port of a cover plate above the circulating ammonia water tank is connected with the waste gas collecting cover through a pipeline, the waste gas collecting cover is connected with the collecting main pipe, the collecting main pipe is connected with an inlet at the lower part of the ammonia collector, an outlet at the upper end of the ammonia collector is connected with the plug-flow folded plate absorption tank through a pipeline, an outlet of the plug-flow folded plate absorption tank is connected with an aeration disc at the lower part of the absorption liquid tank through a; filling sulfide absorbent between the folded plates of the plug flow type folded plate absorption box; the ammonia collector had a particulate filler of modified CaCl 2. The invention optimizes and integrates the treatment modes of tar in coking, metallurgy and coal industries and waste gas of various ammonia water storage tanks, and has the advantages of small investment, small occupied area, simple operation and the like while ensuring the purification effect.

Description

Treatment system and process suitable for waste gas of circulating ammonia water pool of coking plant
Technical Field
The invention belongs to the field of waste gas treatment, and is applied to the waste gas treatment of a circulating ammonia water tank in the coking, metallurgy and coal industries; in particular to a treatment system and a treatment process suitable for the waste gas of a circulating ammonia water pool of a coking plant.
Background
A large amount of ammonia water can be used in the processes of gas washing, cooling, purification, chemical product recovery and refining. The coking plant is often provided with a circulating ammonia water tank or an ammonia water tank for storing ammonia water. Due to liquid level fluctuation and breathing exhaust, in the storage process, waste gas with the characteristics of low concentration, large air quantity, high odor concentration, stable and continuous exhaust and the like can be emitted, and the waste gas mainly comprises hydrogen sulfide, ammonia gas and a small amount of VOCs waste gas mainly comprising hydrogen cyanide, tar, naphthalene, benzene series, polycyclic aromatic hydrocarbon, heterocyclic aromatic hydrocarbon and the like. VOCs (volatile organic compounds) are a generic term for all organic compounds having a vapor pressure of not less than 0.01kPa at 20 ℃ or having volatility under specific applicable conditions. The long-term inhalation of such gases poses serious hazards to the health of workers and surrounding residents and the atmospheric environment. The common treatment methods of the waste gas include absorption method, adsorption method, catalysis method, combustion method, condensation method and the like, and various process combinations. The comprehensive treatment scheme for various waste gases is various, but the high-efficiency treatment technology cannot be provided for the waste gases in the circulating ammonia water pool with the characteristics of low concentration, large air volume, high odor concentration and the like.
The xuhaiqing et al introduced a treatment process of 'water washing absorption, ammonia recovery and hydrogen combustion' in the 'current development of technology for treating ammonia-containing hydrogen-containing waste gas in LED industry'. The process is suitable for treating waste gas in a circulating ammonia water tank because the concentration of the ammonia gas is high; liu Yanjun in "design and application of waste gas treatment process units in ammonia water tank area" thesis has proposed the problem existing in the aspect of waste gas treatment of the condensation production area of the wine steel coking plant, and has proposed the treatment scheme taking the scrubber as the main body, this scheme is simple to regard water as absorbent, can only absorb ammonia, some hydrogen sulfide and a small part of VOCs, the treatment effect is not good; in CN111991994A, a treatment method for volatilizing ammonia is provided, ammonia generated in the production and synthesis processes of urea is recycled, and the ammonia recycling effect is good, but a large amount of absorption liquid is generated in the treatment process and needs to be treated again. CN109173615A provides a method and a device for treating tail gas of an ammonia tank of a coke-oven plant, which uses water as an absorbent and properly treats the residual tail gas. However, the purified tail gas still contains a large amount of harmful components, and the secondary utilization difficulty of the regeneration tower is high.
Analyzing the prior art, the defects can be collated as follows: low treatment efficiency, high running cost, complex operation, large investment, large occupied area and the like.
Disclosure of Invention
The invention provides a treatment system and a treatment process suitable for waste gas of a circulating ammonia water tank of a coking plant, which are optimized and integrated aiming at treatment modes of tar in coking, metallurgy and coal industries and waste gas of various ammonia water storage tanks, and have the advantages of small investment, small occupied area, simple operation and the like while ensuring the purification effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a treatment system suitable for waste gas of a circulating ammonia water pool of a coking plant comprises a waste gas collecting cover, a collecting main pipe, an ammonia absorber, a plug-flow folded plate absorption box and an absorption liquid pool, wherein an exhaust port of a cover plate above the circulating ammonia water pool is connected with the waste gas collecting cover through a pipeline; filling sulfide absorbent between the folded plates of the plug flow type folded plate absorption box; the ammonia collector is provided with modified CaCl2A particulate filler.
The ammonia absorber is provided with a filler supporting layer, and the modified CaCl2The particle filler is filled in the filler support layer.
And a check valve is arranged on a connecting pipeline between the plug flow type folded plate absorption box and the absorption liquid pool.
The plug-flow folded plate absorption box is internally provided with a plurality of layers of folded plates, and the distance between the folded plates is 500-2000 mm.
The modified CaCl2The preparation method of the particles comprises the following steps:
1) preparing a carrier: sieving siderite slag with the particle size of 5-10mm, placing the siderite slag in a tube furnace, roasting the siderite slag for 3-10h in an inert atmosphere at the temperature of 200-250 ℃, cooling the siderite slag, adding nitric acid with the concentration of 10-20 wt%, and stirring the mixture until more white precipitates are separated out; washing the surface of the slag with deionized water until the pH value is 6-7, adding diisopropylethylamine and sodium ethoxide which are dissolved by absolute ethyl alcohol, wherein the molar ratio of the diisopropylethylamine to the sodium ethoxide is 1:1, the diisopropylethylamine and the sodium ethoxide account for 2-10% of the mass of the carrier, adding deionized water to the mixture, carrying out ultrasonic treatment for 10-60min, transferring the mixture to a muffle furnace, continuously roasting for 1-4h, and naturally cooling to room temperature;
2) putting the carrier and excessive aqueous hydrogen peroxide solution into a water bath kettle together, wherein the mass concentration of the aqueous hydrogen peroxide solution is 28-32%, stirring for 10-60min at 30-60 ℃, standing for 110-30h, and cleaning with deionized water; respectively adding polyacrylamide and CaCl with the concentration of 20 wt% -30 wt%2The solution is fully stirred, and the polyacrylamide accounts for CaCl24-6 per mill of the volume of the solution, CaCl2Adding solution in the amount of no carrier, vacuum drying at 60-120 deg.C for 1-4 hr to obtain modified CaCl with modified slag as condensation nucleus2And (3) granules.
The preparation method of the sulfide absorbent is as follows:
1) preparing a carrier: sieving siderite slag with the particle size of 5-10mm, placing the siderite slag in a tube furnace, roasting the siderite slag for 3-10h in an inert atmosphere at the temperature of 200-250 ℃, cooling the siderite slag, adding nitric acid with the concentration of 10-20 wt%, and stirring the mixture until no more white precipitate is separated out; washing the surface of the slag with deionized water until the pH value is 6-7, adding diisopropylethylamine and sodium ethoxide which are dissolved by absolute ethyl alcohol, wherein the molar ratio of the diisopropylethylamine to the sodium ethoxide is 1:1, the diisopropylethylamine and the sodium ethoxide account for 2% -10% of the mass of the carrier, adding deionized water to immerse the mixture, carrying out ultrasonic treatment for 10-60min, transferring the mixture to a muffle furnace, continuing to roast for 1-4h, and naturally cooling to room temperature;
2) putting the carrier and excessive sodium hydroxide into a reaction kettle together, setting the temperature of an oven at 50-100 ℃, heating for 1-3h together, naturally cooling, transferring to a vacuum drying oven, and drying at normal temperature for 3-9 h.
The VOCs absorbent is prepared from the following raw materials in parts by weight: 0.1-0.5 part of sodium benzoate, 1.0-1.5 parts of cold methanol, 1.0-1.5 parts of butanediol, 0.01-0.5 part of diethylhydroxylamine, 0.01-0.5 part of polysorbate-80, 1-10 parts of solubilizer, 20-30 parts of liquid paraffin and 50-80 parts of washing oil; the solubilizer is one or more of polyethylene glycol methyl ether, triethanolamine, polysiloxane-polyalkoxy ether copolymer, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan monopalmitate and ethanol.
The preparation method of the VOCs absorbent comprises the following steps:
1) adding ethanol into a beaker, heating to 30-60 ℃ by using a water bath kettle with a stirring function, adding sodium benzoate, and continuously adding ethanol while stirring until the sodium benzoate is completely dissolved, wherein the solution is marked as a solution A;
2) fully stirring cold methanol, butanediol, diethylhydroxylamine and liquid paraffin, and adding the solution A at the speed of 0.1-3g/min while stirring to obtain a solution B, wherein the viscosity of the solution B is 2000-3000 cP;
3) and (3) stirring and heating the solution B to 60-70 ℃, adding washing oil, adding polysorbate-80 and a solubilizer in the continuous stirring process, and finishing the preparation of the VOCs absorbent after the viscosity of the mixed solution is 10-50 cP.
The process adopts the treatment system suitable for the waste gas of the circulating ammonia water tank of the coke-oven plant, and comprises the following process steps:
1) the circulating ammonia water tanks are communicated with each other in a gas phase, the waste gas of the whole ammonia water tank can be collected by taking gas from the cover plates of the water tanks on one side of the ammonia water tank and collecting the waste gas of the circulating ammonia water tank to the waste gas collecting cover from the discharge ports on the cover plates of the water tanks;
2) the waste gas in the waste gas collecting hood is sent into an ammonia collector through a collecting main pipe, and the waste gas passes through modified CaCl2Removing ammonia gas in the waste gas after the particle filler is purified;
3) the waste gas after ammonia removal enters a plug flow type folded plate absorption box and is absorbed by a sulfide absorbent, so that sulfides in the gas are removed;
4) the waste gas after ammonia and sulfide removal enters from a non-return aeration disc at the lower part of the absorption liquid pool, organic matters in the waste gas are removed by bubbling absorption of VOCs absorbent, and the purified gas is discharged from the top of the absorption liquid pool.
Compared with the prior art, the invention has the beneficial effects that:
1) the invention applies a selective absorption adsorption purification system to treat waste gas step by step, and has ideal purification effect. The purification efficiency reaches more than 98 percent, the occupied area of the equipment is small, the corrosion is prevented, the maintenance is convenient, and the secondary pollution is not generated;
2) the ammonia absorber occupies a small area, 10000-20000m3The treatment capacity/h occupies about 50m of the floor area2The absorbent is modified CaCl2The granules react with ammonia gas to generate calcium octaminochloride (CaCl)2·8NH3) Not only the absorption capacity is large, but also the absorption rate can be greatly improved after modification. The saturated absorbent can be regenerated at 60-70 ℃, and concentrated ammonia gas is recovered;
3) the plug-flow folded plate adsorption box greatly improves the contact area of the waste gas and the sulfide absorbent. The absorbent using the slag as the carrier is adopted, so that the waste resources are recycled, and a good absorption effect is achieved. The sulfide absorbent has large absorption capacity, can be dissolved in water for regeneration after saturation, and can purify and recover useful substances, wherein the solution is crude sodium sulfide;
4) the absorption liquid is suitable for absorbing VOCs, the saturated capacity of the absorption liquid is large, the absorption liquid can be recycled in a certain period, and the saturated absorption liquid can be directly doped in tar, so that the deep processing of the tar is not influenced, and waste liquid is not generated;
5) the process has good treatment effect on the waste gas in the circulating ammonia water tank of the coking plant, and is also suitable for similar waste gas. Through adjusting the sequence, each unit device can adapt to different kinds of tail gas treatment, the energy consumption is less, the cost is low, the pollution is less, the emission requirement is met, and the investment and the operating cost of the purifying device are reduced.
Drawings
FIG. 1 is a process schematic of the system of the present invention.
In the figure: 1-cover plate, 2-ammonia water pool, 3-CaCl2The method comprises the following steps of particle filling, 4-ammonia absorber, 5-absorption main pipe, 6-impeller high-pressure fan, 7-folded plate, 8-plug flow type folded plate absorption box, 9-check valve, 10-aeration disc, 11-absorption liquid pool, 12-absorption liquid and 13-waste gas collection cover.
Detailed Description
The invention will now be described in further detail with reference to the following examples, which are given for the purpose of illustration only and are not intended to limit the scope of the invention. The test methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents and the like used in the following examples are commercially available without otherwise specified.
A treatment system suitable for waste gas of a circulating ammonia water tank of a coking plant comprises a waste gas collecting cover 13, a collecting main pipe 5, an ammonia absorber 4, a plug-flow folded plate absorption box 8 and an absorption liquid tank 11, wherein an exhaust port of a cover plate 1 above a circulating ammonia water tank 2 is connected with the waste gas collecting cover 13 through a pipeline, the waste gas collecting cover 13 is connected with the collecting main pipe 5, the collecting main pipe 5 is connected with an inlet at the lower part of the ammonia collector 4, an outlet at the upper end of the ammonia collector 4 is connected with the plug-flow folded plate absorption box 8 through a pipeline, an outlet of the plug-flow folded plate absorption box 8 is connected with an aeration disc 10 at the lower part of the absorption liquid tank 11 through a pipeline, and the aeration disc; sulfide absorbent is filled between the folded plates 7 of the plug flow type folded plate absorption box 8; the ammonia collector 4 is provided with modified CaCl2 A particulate filler 3.
The ammonia absorber 4 is provided with a filler supporting layer, and the modified CaCl2The particulate filler 3 is filled in the filler support layer.
A check valve 9 is arranged on a connecting pipeline between the plug flow type folded plate absorption box 8 and the absorption liquid pool 11.
The plug-flow folded plate absorption box 8 is internally provided with a plurality of folded plates 7, and the distance between the folded plates 7 is 500-2000 mm.
The modified CaCl2The preparation method of the particles comprises the following steps:
1) preparing a carrier: sieving siderite slag with particle size of 5-10mm, placing in a tubular furnace, roasting at 250 deg.C for 3-10h in inert atmosphere, cooling, adding 10-20 wt% nitric acid, stirring until no more white precipitate is separated out, and the cation symbiotic with siderite may have Bi2+、Ba2+Ammonium compounds and the like, and the surface commensals are replaced by nitric acid, which is beneficial to increasing the specific surface and fully stirring until no white precipitate is continuously separated out; washing the surface of the slag with deionized water until the pH value is 6-7, adding diisopropylethylamine and sodium ethoxide which are dissolved by a small amount of absolute ethyl alcohol, wherein the molar ratio of the diisopropylethylamine to the sodium ethoxide is 1:1, the diisopropylethylamine and the sodium ethoxide account for 2% -10% of the mass of the carrier, adding deionized water to the mixture, carrying out ultrasonic treatment for 10-60min, transferring the mixture to a muffle furnace, continuing to roast for 1-4h, and naturally cooling to room temperature;
2) putting the carrier and excessive aqueous hydrogen peroxide solution into a water bath kettle together, wherein the mass concentration of the aqueous hydrogen peroxide solution is 28-32%, stirring for 10-60min at 30-60 ℃, standing for 110-30h, and cleaning with deionized water; respectively adding polyacrylamide and CaCl with the concentration of 20 wt% -30 wt%2The solution is fully stirred, and the polyacrylamide accounts for CaCl24-6 per mill of the volume of the solution, CaCl2Adding solution in the amount of no carrier, vacuum drying at 60-120 deg.C for 1-4 hr to obtain modified CaCl with modified slag as condensation nucleus2And (3) granules.
The preparation method of the sulfide absorbent is as follows:
1) preparing a carrier: sieving siderite slag with particle size of 5-10mm, placing in a tube furnace, roasting at 250 deg.C for 3-10h in inert atmosphere, cooling, adding 10-20 wt% nitric acid, and stirring until no more white precipitate is separated out (cation coexisting with siderite may have Bi)2+、Ba2+Ammonium compounds and the like, and the surface commensals are replaced by nitric acid, which is beneficial to increasing the specific surface and is fully stirred until no white precipitate is separated out continuously); washing the surface of the slag with deionized water to pH 6-7, adding diisopropylethylamine and sodium ethoxide dissolved with small amount of anhydrous ethanol, wherein the molar ratio of the diisopropylethylamine to the sodium ethoxide is 1:1, and the diisopropyl ethyl amine isEthylamine and sodium ethoxide account for 2-10% of the mass of the carrier), adding deionized water to the mixture, performing ultrasonic treatment for 10-60min, transferring the mixture to a muffle furnace, continuously roasting for 1-4h, and naturally cooling to room temperature;
2) putting the carrier and excessive sodium hydroxide into a reaction kettle together, setting the temperature of an oven at 50-100 ℃, heating for 1-3h together, naturally cooling, transferring to a vacuum drying oven, and drying at normal temperature for 3-9 h.
The VOCs absorbent is prepared from the following raw materials in parts by weight: 0.1-0.5 part of sodium benzoate, 1.0-1.5 parts of cold methanol, 1.0-1.5 parts of butanediol, 0.01-0.5 part of diethylhydroxylamine, 0.01-0.5 part of polysorbate-80, 1-10 parts of solubilizer, 20-30 parts of liquid paraffin and 50-80 parts of washing oil; the solubilizer is one or more of polyethylene glycol methyl ether, triethanolamine, polysiloxane-polyalkoxy ether copolymer, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan monopalmitate and ethanol.
The preparation method of the VOCs absorbent comprises the following steps:
1) adding ethanol into a beaker, heating to 30-60 ℃ by using a water bath kettle with a stirring function, adding sodium benzoate, and continuously adding ethanol while stirring until the sodium benzoate is completely dissolved, wherein the solution is marked as a solution A;
2) fully stirring cold methanol, butanediol, diethylhydroxylamine and liquid paraffin, and adding the solution A at the speed of 0.1-3g/min while stirring to obtain a solution B, wherein the viscosity of the solution B is 2000-3000 cP;
3) and (3) stirring and heating the solution B to 60-70 ℃, adding washing oil, adding polysorbate-80 and a solubilizer in the continuous stirring process, and finishing the preparation of the VOCs absorbent after the viscosity of the mixed solution is 10-50 cP.
The process adopts the treatment system suitable for the waste gas of the circulating ammonia water tank of the coke-oven plant, and comprises the following process steps:
1) the circulating ammonia water tanks 2 are communicated with each other in a gas phase, the waste gas of the whole ammonia water tank 2 can be collected by taking gas from the water tank cover plates 1 of all rows from one side of the ammonia water tank and collecting the waste gas of the circulating ammonia water tank 2 to the waste gas collecting cover 13 from the discharge ports on the water tank cover plates 1;
2) the waste gas in the waste gas collecting hood 13 is sent into an ammonia collector 4 through a collecting main pipe 5, and the waste gas passes through modified CaCl2After the particle filler 3 is purified, removing ammonia gas in the waste gas;
3) the waste gas after ammonia removal enters a plug flow type folded plate absorption box 8 and is absorbed by a sulfide absorbent to remove sulfides in the gas;
4) the waste gas after ammonia and sulfide removal enters from the non-return aeration disc 10 at the lower part of the absorption liquid pool 11, organic matters in the waste gas are removed by bubbling absorption of VOCs absorbent, and the purified gas is discharged from the top of the absorption liquid pool 11.
Example 1:
a treatment system suitable for waste gas of a circulating ammonia water tank of a coking plant comprises a waste gas collecting cover 13, a collecting main pipe 5, an ammonia absorber 4, a plug-flow folded plate absorption box 5 and an absorption liquid tank 11, wherein an exhaust port of a cover plate 1 above a circulating ammonia water tank 2 is connected with the waste gas collecting cover 13 through a pipeline, the waste gas collecting cover 13 is connected with the collecting main pipe 5, the collecting main pipe 5 is connected with an inlet at the lower part of the ammonia collector 4, an outlet at the upper end of the ammonia collector 4 is connected with a plug-flow folded plate absorption box 8 through a pipeline, an outlet of the plug-flow folded plate absorption box 8 is connected with an aeration disc 10 at the lower part of the absorption liquid tank 11 through a pipeline, and the aeration disc; sulfide absorbent is filled between the folded plates 7 of the plug flow type folded plate absorption box 8; the ammonia collector 4 is provided with modified CaCl2A particulate filler 3.
A plurality of layers of folded plates 7 are arranged in the plug-flow type folded plate absorption box 8, and the distance between the folded plates 7 is 1000 mm.
Modified CaCl2The preparation method of the particle filler comprises the following steps:
1) preparing a carrier, screening siderite slag with the size of 5-10mm, placing the siderite slag in a tube furnace, roasting for 8 hours at 200 ℃ in an inert atmosphere, cooling, adding nitric acid with the concentration of 15 wt%, and stirring for a certain time until no more white precipitate is separated out; washing the surface of the slag with deionized water until the pH value is 6-7, adding diisopropylethylamine and sodium ethoxide which are dissolved by a small amount of absolute ethyl alcohol, wherein the molar ratio of the diisopropylethylamine to the sodium ethoxide is 1:1, the diisopropylethylamine and the sodium ethoxide account for 2-10% of the mass of the carrier, adding deionized water to the mixture, performing ultrasonic treatment for 30min, transferring the mixture to a muffle furnace, continuing to roast for 3h, and naturally cooling to room temperature;
2) taking a proper amount of carrier, putting the carrier and excessive hydrogen peroxide aqueous solution into a water bath kettle together, wherein the mass concentration of the hydrogen peroxide aqueous solution is 30%, stirring the carrier and the excessive hydrogen peroxide aqueous solution for 30min at 40 ℃, and standing the carrier for 20 h. And cleaning with deionized water. Respectively adding polyacrylamide and CaCl with the concentration of 25 wt%2The solution is fully stirred, and the polyacrylamide accounts for CaCl2CaCl 5 ‰ of the volume of the solution2The solution is added in an amount of submerging the carrier, and is dried for 3 hours in vacuum at the temperature of 90 ℃ to obtain modified CaCl taking the modified slag as condensation nucleus2And (3) granules.
The preparation method of the sulfide absorbent comprises the following steps:
1) the sulfide absorbent carrier adopts modified CaCl2Preparation method of particulate filler the modified slag carrier prepared in step 1).
2) Taking a proper amount of carrier, putting the carrier and excessive sodium hydroxide into a reaction kettle together, setting the temperature of an oven at 100 ℃, heating for 2 hours, naturally cooling, transferring to a vacuum drying oven, and drying at normal temperature for 6 hours.
The absorption liquid pool is a VOCs absorbent suitable for a coking plant, and every 100g of the absorbent comprises 0.1g of sodium benzoate, 1.0g of cold methanol, 1.0g of butanediol, 0.02g of diethylhydroxylamine, 0.3g of polysorbate-80, 8g of solubilizer, 20g of liquid paraffin and the balance of wash oil. The solubilizer is one or more of polyethylene glycol methyl ether, triethanolamine, polysiloxane-polyalkoxy ether copolymer, polyoxyethylene fatty acid, polyoxyethylene sorbitan monopalmitate and ethanol.
The preparation process of the VOCs absorbent is as follows:
1) adding appropriate amount of ethanol into beaker, heating to 45 deg.C with water bath kettle with stirring function, adding sodium benzoate after temperature is stable, and stirring for 30 min. And continuously adding ethanol in the stirring and heating process to ensure that the sodium benzoate is dissolved. Denoted as solution A.
2) After cold methanol, butanediol, diethylhydroxylamine and liquid paraffin were sufficiently stirred, the solution A was added at a rate of 0.5g/min under stirring to obtain a solution B. Solution B viscosity reached 2670cP at this point.
3) And (3) stirring and heating the solution B to 60 ℃, adding the washing oil, and adding a proper amount of polysorbate-80 and a solubilizer in the process of continuous stirring. And after the viscosity of the mixed solution reaches 15cP, the preparation of the VOCs absorbent is finished.
A treatment process suitable for waste gas of a circulating ammonia water pool of a coking plant comprises the following process steps:
1) the circulating ammonia water tank 2 is communicated with each other in a gas phase, the waste gas of the whole ammonia water tank can be collected by taking gas from each row of water tank cover plates 1 from one side of the ammonia water tank 2 and collecting the waste gas of the circulating ammonia water tank 2 to a waste gas collecting cover 13 from a discharge port on the water tank cover plates 1;
2) the waste gas in the waste gas collecting hood 13 is sent into an ammonia collector 4 through a collecting main pipe 5, and the waste gas passes through modified CaCl2After the particle filler 3 is purified, removing ammonia gas in the waste gas;
3) the waste gas after ammonia removal enters a plug flow type folded plate absorption box 8 and is absorbed by a sulfide absorbent to remove sulfides in the gas;
4) the waste gas after ammonia and sulfide removal enters from a non-return aeration disc 10 at the lower part of the absorption liquid pool 11, organic matters in the waste gas are removed by bubbling absorption through a VOCs absorbent 12, and the purified gas is discharged from the top of the absorption liquid pool 11.
The invention relates to a treatment system and a treatment process suitable for waste gas of a circulating ammonia water pool of a coking plant, which take an absorption-adsorption principle as guidance and can efficiently treat the waste gas of the circulating ammonia water pool in coking, metallurgy and coal industries. The process is simple and reasonable, the treatment efficiency is high, the investment and operation cost is low, and the energy consumption and treatment effect are superior to those of the common technologies such as a direct burning method; the operation difficulty is low, and the automatic control is easy to realize.

Claims (8)

1. The utility model provides a processing system suitable for circulation aqueous ammonia pond waste gas of coke-oven plant, its characterized in that collects cover, collection house steward, ammonia absorber, pushes away STREAMING folded plate absorption box, absorption liquid pond including waste gas, circulation aqueous ammonia pond top apron gas vent passes through pipe connection waste gas and collects the cover, waste gas is collected the cover and is connected and collect the house steward, collect the lower part entry of house steward connection ammonia collector, the upper end export of ammonia collector pushes away STREAMING through pipe connection through the pipe connection and pushes away the STREAMING folded plateThe outlet of the plug-flow type folded plate absorption box is connected with an aeration disc at the lower part of the absorption liquid pool through a pipeline, and the aeration disc is immersed in the VOCs absorbent; filling sulfide absorbent between the folded plates of the plug flow type folded plate absorption box; the ammonia collector is provided with modified CaCl2A particulate filler.
2. The system of claim 1, wherein the ammonia absorber comprises a support layer for packing, and the modified CaCl comprises2The particle filler is filled in the filler support layer.
3. The system of claim 1, wherein a check valve is disposed on the connecting pipe between the plug flow type folded plate absorption box and the absorption liquid pool.
4. The system for treating the waste gas of the circulating ammonia water pool of the coke-oven plant as claimed in claim 1, wherein the modified CaCl2The preparation method of the particles comprises the following steps:
1) preparing a carrier: sieving siderite slag with the particle size of 5-10mm, placing the siderite slag in a tube furnace, roasting the siderite slag for 3-10h in an inert atmosphere at the temperature of 200-250 ℃, cooling the siderite slag, adding nitric acid with the concentration of 10-20 wt%, and stirring the mixture until more white precipitates are separated out; washing the surface of the slag with deionized water until the pH value is 6-7, adding diisopropylethylamine and sodium ethoxide which are dissolved by absolute ethyl alcohol, wherein the molar ratio of the diisopropylethylamine to the sodium ethoxide is 1:1, the diisopropylethylamine and the sodium ethoxide account for 2% -10% of the mass of the carrier, adding deionized water to immerse the mixture, carrying out ultrasonic treatment for 10-60min, transferring the mixture to a muffle furnace, continuing to roast for 1-4h, and naturally cooling to room temperature;
2) putting the carrier and excessive aqueous hydrogen peroxide solution into a water bath kettle together, wherein the mass concentration of the aqueous hydrogen peroxide solution is 28-32%, stirring for 10-60min at 30-60 ℃, standing for 110-30h, and cleaning with deionized water; respectively adding polyacrylamide and CaCl with the concentration of 20 wt% -30 wt%2Stirring the solution thoroughly, polypropyleneEnamides in CaCl24-6 per mill of the volume of the solution, CaCl2Adding solution in the amount of no carrier, vacuum drying at 60-120 deg.C for 1-4 hr to obtain modified CaCl with modified slag as condensation nucleus2And (3) granules.
5. The system of claim 1, wherein the sulfide absorbent is prepared by the following steps:
1) preparing a carrier: sieving siderite slag with the particle size of 5-10mm, placing the siderite slag in a tube furnace, roasting the siderite slag for 3-10h in an inert atmosphere at the temperature of 200-250 ℃, cooling the siderite slag, adding nitric acid with the concentration of 10-20 wt%, and stirring the mixture until no more white precipitate is separated out; washing the surface of the slag with deionized water until the pH value is 6-7, adding diisopropylethylamine and sodium ethoxide which are dissolved by absolute ethyl alcohol, wherein the molar ratio of the diisopropylethylamine to the sodium ethoxide is 1:1, the diisopropylethylamine and the sodium ethoxide account for 2% -10% of the mass of the carrier, adding deionized water to immerse the mixture, carrying out ultrasonic treatment for 10-60min, transferring the mixture to a muffle furnace, continuing to roast for 1-4h, and naturally cooling to room temperature;
2) putting the carrier and excessive sodium hydroxide into a reaction kettle together, setting the temperature of an oven at 50-100 ℃, heating for 1-3h together, naturally cooling, transferring to a vacuum drying oven, and drying at normal temperature for 3-9 h.
6. The system of claim 1, wherein the VOCs absorbent is prepared from the following raw materials in parts by weight: 0.1-0.5 part of sodium benzoate, 1.0-1.5 parts of cold methanol, 1.0-1.5 parts of butanediol, 0.01-0.5 part of diethylhydroxylamine, 0.01-0.5 part of polysorbate-80, 1-10 parts of solubilizer, 20-30 parts of liquid paraffin and 50-80 parts of washing oil; the solubilizer is one or more of polyethylene glycol methyl ether, triethanolamine, polysiloxane-polyalkoxy ether copolymer, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan monopalmitate and ethanol.
7. The system of claim 6, wherein the VOCs absorbent is prepared by the following steps:
1) adding ethanol into a beaker, heating to 30-60 ℃ by using a water bath kettle with a stirring function, adding sodium benzoate, and continuously adding ethanol while stirring until the sodium benzoate is completely dissolved, wherein the solution is marked as a solution A;
2) fully stirring cold methanol, butanediol, diethylhydroxylamine and liquid paraffin, and adding the solution A at the speed of 0.1-3g/min while stirring to obtain a solution B, wherein the viscosity of the solution B is 2000-3000 cP;
3) and (3) stirring and heating the solution B to 60-70 ℃, adding washing oil, adding polysorbate-80 and a solubilizer in the continuous stirring process, and finishing the preparation of the VOCs absorbent after the viscosity of the mixed solution is 10-50 cP.
8. A process for treating the waste gas of the circulating ammonia water pool of the coke-oven plant, which is characterized in that the process adopts the treatment system of the claim 1, and the process comprises the following steps:
1) collecting the waste gas of the circulating ammonia water pool to a waste gas collecting cover from a discharge port on a water tank cover plate;
2) the waste gas in the waste gas collecting hood is sent into an ammonia collector through a collecting main pipe, and the waste gas passes through modified CaCl2Removing ammonia gas in the waste gas after the particle filler is purified;
3) the waste gas after ammonia removal enters a plug flow type folded plate absorption box and is absorbed by a sulfide absorbent, so that sulfides in the gas are removed;
4) the waste gas after ammonia and sulfide removal enters from a non-return aeration disc at the lower part of the absorption liquid pool, organic matters in the waste gas are removed by bubbling absorption of VOCs absorbent, and the purified gas is discharged from the top of the absorption liquid pool.
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CN116617806B (en) * 2023-05-23 2023-11-03 迁安市宏奥工贸有限公司 Method for treating waste gas of coking plant

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