CN110947300A - Desulfurization method, desulfurization apparatus, and desulfurization mixture - Google Patents

Desulfurization method, desulfurization apparatus, and desulfurization mixture Download PDF

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CN110947300A
CN110947300A CN201911081907.4A CN201911081907A CN110947300A CN 110947300 A CN110947300 A CN 110947300A CN 201911081907 A CN201911081907 A CN 201911081907A CN 110947300 A CN110947300 A CN 110947300A
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desulfurization
mixture
gas
activated carbon
carbon catalyst
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刘勇军
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Sichuan University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides

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Abstract

The invention discloses a desulfurization method, desulfurization equipment and a desulfurization mixture. One such desulfurization process comprises the following that occurs in the desulfurization reaction unit: receiving a gas to be treated containing sulfur dioxide and oxygen and introducing them into a desulfurization mixture; absorbing sulfur dioxide and oxygen by water serving as a continuous phase in the desulfurization mixture and forming a dissolved sulfur source and an oxygen source; the active carbon catalyst particles serving as a dispersed phase in the desulfurization mixture enable a sulfur source and an oxygen source on the surface of the dispersed phase to generate sulfuric acid; and discharging the tail gas treated from the desulfurization mixture. The desulfurization method has obvious substantial difference with the desulfurization mechanism of the traditional fixed bed activated carbon-based catalytic desulfurization technology, and can effectively overcome the defect that the sulfur content in the traditional fixed bed activated carbon-based catalytic desulfurization technology is H2SO4The catalytic reaction rate rapidly decreases after the occurrence in the pores of the activated carbon catalyst.

Description

Desulfurization method, desulfurization apparatus, and desulfurization mixture
Technical Field
The invention relates to a flue gas desulfurization technology, in particular to a desulfurization method, desulfurization equipment and a desulfurization mixture.
Background
The basic principle of the fixed bed active carbon-based catalytic desulfurization technology is that an active carbon catalyst (comprising granular active carbon, modified active carbon or a flue gas desulfurization catalyst taking the active carbon as a carrier and the like) is filled in a fixed bed reactor, and when flue gas passes through the active carbon catalyst, SO in the flue gas2And O2Is absorbed by an active carbon catalyst and is catalytically oxidized into SO3，SO3Further with H in the flue gas2Reaction of O vapor to H2SO4H is generated2SO4Aggregation in the pores of the activated carbon catalyst, resulting in gradual degradation of the performance of the activated carbon catalyst, as H aggregates in the pores of the activated carbon catalyst2SO4After saturation, the activated carbon catalyst needs to be regenerated by acid washing or water washing (for a specific regeneration method, see patent document CN 109453667A). Due to H2SO4The occurrence in the pores of the activated carbon catalyst can greatly reduce SO2And O2Effective diffusion coefficient in activated carbon catalyst (diffusion coefficient of gas molecules in gas phase 10)-2-10-3cm2S, but only 10 in the liquid phase-5cm2In the order of/s), the above-mentioned fixed bed activated carbon-based catalytic desulfurization technique has a problem that the catalytic reaction rate is rapidly decreased.
Disclosure of Invention
The invention aims to provide a desulfurization method, a desulfurization device and a desulfurization mixture which are different from the fixed bed activated carbon-based catalytic desulfurization technology.
In order to achieve the above object, according to one aspect of the present invention, there is provided a desulfurization method. The desulfurization method specifically comprises the following steps: the desulfurization reaction unit receives a gas to be treated comprising sulfur dioxide and oxygen and introduces it into a desulfurization mixture consisting essentially of water and activated carbon catalyst particles, the ratio of the mass of the activated carbon catalyst particles to the mass of the water in the desulfurization mixture being 0.05 to 1 and the specific surface area of the activated carbon catalyst particles being not less than 500m2(ii)/g; the mixture of sulfur dioxide and oxygen in the gas to be treated is desulfurized when the gas to be treated passes through the desulfurization mixture in the desulfurization reaction unitAbsorbing and converting into sulfuric acid in the desulfurization mixture, discharging the treated tail gas from the desulfurization reaction unit, and controlling the flow (m) of the gas to be treated passing through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio of 400-4000h-1(ii) a The solid-liquid separation unit receives the desulfurization mixture which is output by the desulfurization reaction unit and reaches a certain sulfuric acid concentration, and carries out solid-liquid separation treatment on the desulfurization mixture which reaches the certain sulfuric acid concentration, so as to respectively obtain a sulfuric acid product and activated carbon catalyst particles which are used as raw materials of subsequent desulfurization mixtures.
The technical concept of the above desulfurization method is based on the following desulfurization mechanism: because the desulfurization mixture is mainly composed of water and activated carbon catalyst particles, sulfur dioxide and oxygen in the gas to be treated are absorbed by the water when the gas passes through the desulfurization mixture to form a dissolved sulfur source and an oxygen source, and the sulfur source and the oxygen source react to generate sulfuric acid under the catalytic action of the activated carbon catalyst particles, so that desulfurization is realized. The desulfurization mechanism is obviously different from that of the traditional fixed bed activated carbon-based catalytic desulfurization technology in material, and the problem that the traditional fixed bed activated carbon-based catalytic desulfurization technology is H in H can be effectively solved2SO4The catalytic reaction rate rapidly decreases after the occurrence in the pores of the activated carbon catalyst. On the basis, the desulfurization method can practically achieve comprehensive benefits such as higher desulfurization efficiency and the like by the combined configuration of three key technical parameters, namely the mass ratio of the activated carbon catalyst particles to the mass of water, the specific surface area of the activated carbon catalyst particles and the volume ratio of the gas flow to be treated passing through the desulfurization mixture to the volume of the desulfurization mixture.
Specifically, setting the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture to be 0.05 to 1 helps to dissolve sulfur dioxide and oxygen more sufficiently in water and to secure the catalytic reaction effect of the activated carbon catalyst particles on the dissolved sulfur source and oxygen source. When the mass ratio of the activated carbon catalyst particles to the water is less than 0.05, the content of the activated carbon catalyst particles is too low, the provided active sites are insufficient, and the catalytic reaction effect is poor; when activeWhen the ratio of the mass of the carbon catalyst particles to the mass of water is more than 1, the content of water is too low, which is not favorable for the sufficient dissolution of sulfur dioxide and oxygen and is liable to cause the desulfurization mixture to be too viscous and inconvenient for the operation of the desulfurization mixture. The specific surface area of the activated carbon catalyst particles was set to 500m2Above the volume of the active carbon catalyst particles, on one hand, the basic active site requirement of the active carbon catalyst particles of unit mass is ensured, and on the other hand, the active carbon catalyst particles have active carbon catalyst morphology, which shows that the pores of the active carbon catalyst particles are fully exposed, and the influence of the internal diffusion of the active carbon catalyst is favorably eliminated. While the flow rate (m) of the gas to be treated which will pass through said desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio is controlled to 400-4000h-1And the desulfurization effect is further ensured by restricting the relationship between the flow of the gas to be treated and the volume of the desulfurization mixture. Flow rate (m) of gas to be treated while passing through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio of the water to the oil is less than 400h-1In time, the operating economy of the desulfurization process is poor; flow rate (m) of gas to be treated while passing through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio of the two is more than 4000h-1In the case of the conventional desulfurization method, the desulfurization effect is poor. In summary, the desulfurization method can achieve high desulfurization efficiency in practice and achieve good benefits in the aspects of operation economy and the like of the desulfurization method through the combined configuration of three key technical parameters, namely the mass ratio of the activated carbon catalyst particles to the mass of water in the desulfurization mixture, the specific surface area of the activated carbon catalyst particles and the volume ratio of the gas flow to be treated of the desulfurization mixture to the volume of the desulfurization mixture.
As a further optimization or refinement to the above related solution, at least a portion of the oxygen and the sulfur dioxide are native to a generation source of the gas to be treated. In this case, the oxygen in the gas to be treated may be entirely originated from the source of the gas to be treated, or may be partly originated from the source of the gas to be treated and the remaining part may be a part of the gas to be treated by the input of the oxygen supplement gas flow.
As a further optimization or refinement to the above related technical solution, the volume percentage content of oxygen in the gas to be treated is not less than 3%, preferably more than 5%, and more preferably more than 10%.
As a further optimization or refinement to the above related technical solution, the volume percentage of the sulfur dioxide in the gas to be treated is not higher than 3%, preferably not higher than 1%, and more preferably not higher than 0.5%.
As a further optimization or refinement to the above related technical solution, the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture is 0.1 to 0.6.
As a further optimization or refinement to the above related technical solution, the temperature of the desulfurization mixture in the desulfurization reaction unit is 20 to 90 degrees celsius, preferably 30 to 80 degrees celsius, and more preferably 40 to 60 degrees celsius.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from a requirement that all activated carbon catalyst particles can be ensured to pass through a 10-mesh sieve to a requirement that all activated carbon catalyst particles can be ensured to pass through a 2000-mesh sieve.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from a requirement that all activated carbon catalyst particles can be ensured to pass through a 10-mesh sieve to a requirement that all activated carbon catalyst particles can be ensured to pass through a 1000-mesh sieve.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from that all activated carbon catalyst particles can be ensured to pass through a 50-mesh sieve to that all activated carbon catalyst particles can be ensured to pass through a 1000-mesh sieve.
As a further optimization or refinement of the related technical scheme, the solid-liquid separation unit adopts any one of a cyclone separator, a centrifugal filter, a plate-and-frame filter press, a membrane filter and a natural settling tank.
As a further optimization or refinement for the related technical scheme, the active carbon catalyst particles are prepared by grinding at least one of coal active carbon, biomass active carbon, modified active carbon, flue gas desulfurization catalyst taking active carbon as a carrier, waste active carbon desulfurizer after fixed bed active carbon-based catalytic desulfurization and active carbon fiber.
As a further optimization or refinement to the above-mentioned related art solution, the gas to be treated is introduced into the desulfurization mixture with the stirring operation performed on the desulfurization mixture; and/or the gas to be treated and/or the oxygen-supplementary gas stream which is part of the gas to be treated are introduced into the desulfurization mixture by means of aeration in the desulfurization mixture.
As a further optimization or refinement to the above related art solution, the aeration disperses the gas to be aerated in the desulfurization mixture by the micro-porous aeration member having an outlet size of 3 mm or less, 1 mm or less, or 500 μm or less.
As further optimization or refinement of the related technical scheme, the desulfurization reaction unit adopts any one of a spray stirring reactor, a bubbling stirring reactor, a jet bubbling reactor, a stirring turbulent ball reactor and a sieve plate tower.
In order to achieve the above object, according to another aspect of the present invention, there is provided a desulfurization method. The desulfurization method comprises the following steps of: receiving a gas to be treated containing sulfur dioxide and oxygen and introducing them into a desulfurization mixture; absorbing sulfur dioxide and oxygen by water serving as a continuous phase in the desulfurization mixture and forming a dissolved sulfur source and an oxygen source; the active carbon catalyst particles serving as a dispersed phase in the desulfurization mixture enable a sulfur source and an oxygen source on the surface of the dispersed phase to generate sulfuric acid; and discharging the tail gas treated from the desulfurization mixture. The desulfurization method has obvious substantial difference with the desulfurization mechanism of the traditional fixed bed activated carbon-based catalytic desulfurization technology, and can effectively overcome the defect that the sulfur content in the traditional fixed bed activated carbon-based catalytic desulfurization technology is H2SO4The catalytic reaction rate rapidly decreases after the appearance in the pores of the activated carbon catalystTo a problem of (a).
As a further optimization or refinement to the above related solution, at least a portion of the oxygen and the sulfur dioxide are native to a generation source of the gas to be treated. In this case, the oxygen in the gas to be treated may be entirely originated from the source of the gas to be treated, or may be partly originated from the source of the gas to be treated and the remaining part may be a part of the gas to be treated by the input of the oxygen supplement gas flow.
As a further optimization or refinement to the above related technical solution, the volume percentage content of oxygen in the gas to be treated is not less than 3%, preferably more than 5%, and more preferably more than 10%.
As a further optimization or refinement to the above related technical solution, the volume percentage of the sulfur dioxide in the gas to be treated is not higher than 3%, preferably not higher than 1%, and more preferably not higher than 0.5%.
As a further optimization or refinement to the above related technical solution, the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture is 0.05 to 1 and the specific surface area of the activated carbon catalyst particles is not less than 500m2(ii)/g; controlling the flow (m) of gas to be treated through the desulphurisation mixture3H) volume of desulfurized mixture (m)3) The ratio of 400-4000h-1. Therefore, the desulfurization method can practically achieve comprehensive benefits such as higher desulfurization efficiency and the like by the combined configuration of three key technical parameters, namely the mass ratio of the activated carbon catalyst particles to the mass of water, the specific surface area of the activated carbon catalyst particles and the volume ratio of the gas flow to be treated passing through the desulfurization mixture to the volume of the desulfurization mixture.
As a further optimization or refinement to the above related technical solution, the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture is 0.1 to 0.6.
As a further optimization or refinement to the above related technical solution, the temperature of the desulfurization mixture in the desulfurization reaction unit is 20 to 90 degrees celsius, preferably 30 to 80 degrees celsius, and more preferably 40 to 60 degrees celsius.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from a requirement that all activated carbon catalyst particles can be ensured to pass through a 10-mesh sieve to a requirement that all activated carbon catalyst particles can be ensured to pass through a 2000-mesh sieve.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from a requirement that all activated carbon catalyst particles can be ensured to pass through a 10-mesh sieve to a requirement that all activated carbon catalyst particles can be ensured to pass through a 1000-mesh sieve.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from that all activated carbon catalyst particles can be ensured to pass through a 50-mesh sieve to that all activated carbon catalyst particles can be ensured to pass through a 1000-mesh sieve.
As a further optimization or refinement for the related technical scheme, the active carbon catalyst particles are prepared by grinding at least one of coal active carbon, biomass active carbon, modified active carbon, flue gas desulfurization catalyst taking active carbon as a carrier, waste active carbon desulfurizer after fixed bed active carbon-based catalytic desulfurization and active carbon fiber.
As a further optimization or refinement to the above-mentioned related art solution, the gas to be treated is introduced into the desulfurization mixture with the stirring operation performed on the desulfurization mixture; and/or the gas to be treated and/or the oxygen-supplementary gas stream which is part of the gas to be treated are introduced into the desulfurization mixture by means of aeration in the desulfurization mixture.
As a further optimization or refinement to the above related art solution, the aeration disperses the gas to be aerated in the desulfurization mixture by the micro-porous aeration member having an outlet size of 3 mm or less, 1 mm or less, or 500 μm or less.
In order to achieve the above object, according to still another aspect of the present invention, there is provided a desulfurization apparatus. The desulfurization apparatus includes a desulfurization reaction unit, which is a desulfurization reaction unit used in any one of the above desulfurization methods.
As a further optimization or refinement to the above-described related art, the desulfurization reaction unit includes a stirring device that performs a stirring operation on the desulfurization mixture along with introduction of the gas to be treated into the desulfurization mixture; and/or the desulfurization reaction unit comprises an aeration device which introduces the gas to be treated and/or an oxygen supplement gas flow which is a part of the gas to be treated into the desulfurization mixture in a manner of aerating in the desulfurization mixture.
As further optimization or refinement of the related technical scheme, the desulfurization reaction unit adopts any one of a spray stirring reactor, a bubbling stirring reactor, a jet bubbling reactor, a stirring turbulent ball reactor and a sieve plate tower.
As a further optimization or refinement to the above related technical solution, the aeration device includes a micro-porous aeration component, and the size of the air outlet of the micro-porous aeration component is 3 mm or less, 1 mm or less or 500 micrometers or less.
In order to achieve the above object, according to still another aspect of the present invention, there is provided a desulfurization mixture. The desulfurization mixture comprises: water as the continuous phase; activated carbon catalyst particles as a dispersed phase; wherein the ratio of the mass of the activated carbon catalyst particles to the mass of water is 0.05 to 1 and the specific surface area of the activated carbon catalyst particles is not less than 500m2/g。
As a further optimization or refinement to the above related technical solution, the ratio of the mass of the activated carbon catalyst particles to the mass of water is 0.1 to 0.6.
As a further optimization or refinement for the related technical scheme, the active carbon catalyst particles are prepared by grinding at least one of coal active carbon, biomass active carbon, modified active carbon, flue gas desulfurization catalyst taking active carbon as a carrier, waste active carbon desulfurizer after fixed bed active carbon-based catalytic desulfurization and active carbon fiber.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from a requirement that all activated carbon catalyst particles can be ensured to pass through a 10-mesh sieve to a requirement that all activated carbon catalyst particles can be ensured to pass through a 2000-mesh sieve.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from a requirement that all activated carbon catalyst particles can be ensured to pass through a 10-mesh sieve to a requirement that all activated carbon catalyst particles can be ensured to pass through a 1000-mesh sieve.
As a further optimization or refinement of the above related art, the particle size of the activated carbon catalyst particles is in a range from that all activated carbon catalyst particles can be ensured to pass through a 50-mesh sieve to that all activated carbon catalyst particles can be ensured to pass through a 1000-mesh sieve.
As further optimization or refinement of the related technical scheme, the desulfurization mixture further comprises sulfuric acid as a second dispersed phase, wherein the sulfuric acid mass concentration of the sulfuric acid solution in the desulfurization mixture is below 40%; or, sulfuric acid is also included as a second dispersed phase, and the desulfurization mixture is the desulfurization mixture at the beginning of the operation of the desulfurization method, and the sulfuric acid solution in the desulfurization mixture has a sulfuric acid mass concentration of 5 to 30%.
The invention is further described with reference to the following figures and detailed description. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to assist in understanding the invention, and are included to explain the invention and their equivalents and not limit it unduly. In the drawings:
FIG. 1 is a schematic structural view of a part of an embodiment of a desulfurization apparatus of the present invention.
FIG. 2 is a schematic view showing the constitution of an experimental apparatus for experimentally verifying a part of examples of the desulfurization method of the present invention. The reference numbers in fig. 2 are: 1-nitrogen cylinder, 2-sulfur dioxide cylinder, 3-oxygen cylinder, 4-mass flow meter, 5-gas mixing cylinder, 6-three-way valve, 7-humidifying cylinder, 8-constant temperature water bath, 9-constant temperature water bath, 10-desulfurization reactor, 11-condensing cylinder, 12-ice bath, 13-flue gas analyzer, 14-wet gas flow meter, 15-sulfur dioxide tail gas absorption cylinder.
FIGS. 3 to 16 are graphs showing the relationship between desulfurization time and desulfurization efficiency in each experimental example in some examples of the desulfurization method of the present invention.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying drawings. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is described in detail with reference to the accompanying drawings, it is to be noted that:
technical solutions and technical features provided in the respective portions including the following description in the present invention may be combined with each other without conflict.
In addition, the embodiments of the present invention described in the following description are generally only a partial embodiment of the present invention, and not all embodiments, and therefore, all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention should fall within the protection scope of the present invention.
With respect to the terms and units in the present invention: the terms "comprising," "including," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions. In addition, other related terms and units in the invention can be reasonably construed based on the related contents of the invention.
FIG. 1 is a schematic structural view of a part of an embodiment of a desulfurization apparatus of the present invention. As shown in fig. 1, the desulfurization apparatus includes a desulfurization reaction unit 100, and the desulfurization reaction unit 100 can be used for implementing the following desulfurization methods, including: receiving a gas 300 to be treated containing sulfur dioxide and oxygen and introducing them into the desulfurization mixture 110; water 112, as the continuous phase in the desulfurization mixture 110, absorbs sulfur dioxide and oxygen and forms a source of dissolved sulfur and oxygen; the activated carbon catalyst particles 111 as a dispersed phase in the desulfurization mixture 110 cause a sulfur source and an oxygen source on the surface of the dispersed phase to generate sulfuric acid; the tail gas 320 treated from the desulfurization mixture 110 is discharged.
The "continuous phase" refers to a substance in which other substances are dispersed in a dispersion system; and the term "dispersed phase" refers to the material dispersed in the dispersion. Since the desulfurization method uses the desulfurization mixture 110, the desulfurization method should be classified as "wet desulfurization" and the conventional fixed bed activated carbon-based catalytic desulfurization technology as "dry desulfurization". The inventors of the present invention considered through research that, in the above-mentioned "water 112 as a continuous phase in the desulfurization mixture 110 absorbs sulfur dioxide and oxygen and forms a dissolved sulfur source and an oxygen source" and "the activated carbon catalyst particles 111 as a dispersed phase in the desulfurization mixture 110 cause the sulfur source and the oxygen source on the surface of the dispersed phase to generate sulfuric acid", sulfur dioxide in the gas 300 to be treated becomes dissolved sulfur dioxide or chemically reacts with water to generate H2SO3(dissolved Sulfur dioxide and H2SO3Both "sulfur sources"), dissolved sulfur dioxide and H2SO3Then reacts with dissolved oxygen (i.e., "oxygen source") in water under the catalytic action of the activated carbon catalyst particles 111 to produce sulfuric acid.
Obviously, the desulfurization mechanism of the desulfurization method is obviously substantially different from that of the traditional fixed bed activated carbon-based catalytic desulfurization technology, and the condition that the gas phase is diffused in the activated carbon catalyst does not exist basically in the desulfurization method, so that the problem that the conventional fixed bed activated carbon-based catalytic desulfurization technology is used as H in the traditional fixed bed activated carbon-based catalytic desulfurization technology can be effectively solved2SO4The catalytic reaction rate rapidly decreases after the occurrence in the pores of the activated carbon catalyst.
The desulfurization reaction unit 100 may specifically employ any suitable gas-liquid-solid three-phase reactor, such as a spray reactor, a bubble reactor, a jet bubble reactor, a turbulent ball reactor or a sieve plate tower (in industrial applications, the desulfurization reaction unit 100 may be a sieve plate tower). In some embodiments of the invention, the desulfurization reaction unit respectively adopts a spray stirring reactor, a bubble stirring reactor, a jet bubble reactor and a stirring turbulent ball reactor, the reactors are all added with the stirring function of the desulfurization mixture 110 on the basis of the corresponding original existing reactors (which can be realized by various known mechanical stirring devices), for example, the spray stirring reactor is formed by adding a stirring device to the existing spray reactor in the region for storing the desulfurization mixture 110 at the bottom of the reactor, in this way, the gas 300 to be treated can be introduced into the desulfurized mixture 110 with the stirring operation performed on the desulfurized mixture 110, to promote dissolution of sulfur dioxide and oxygen in water, to promote diffusion of the sulfur source and oxygen source to the surface of the activated carbon catalyst particles, and to promote diffusion of the sulfuric acid produced by the reaction into the liquid phase bulk of the desulfurization mixture.
As shown in fig. 1, the desulfurization apparatus may further include a solid-liquid separation unit 200, where the solid-liquid separation unit 200 is configured to receive the desulfurization mixture 110 reaching a certain sulfuric acid concentration output by the desulfurization reaction unit 100 and perform a solid-liquid separation treatment on the desulfurization mixture 110 reaching the certain sulfuric acid concentration, so as to obtain a sulfuric acid product 400 and activated carbon catalyst particles 111 serving as raw materials of a subsequent desulfurization mixture, respectively.
The solid-liquid separation unit 200 may employ any suitable solid-liquid separation equipment/facility, such as a cyclone, a centrifugal filter, a plate and frame filter press, a membrane filter, or a natural settling tank. The solid-liquid separation unit 200 and the desulfurization reaction unit 100 may be two separate devices/facilities or may be combined devices/facilities. For example, the desulfurization reaction unit 100 employs a spray agitation reactor, and a solid-liquid separation structure having a function similar to that of a sedimentation tank is provided at the bottom of the spray agitation reactor as the solid-liquid separation unit 200, so that the desulfurization reaction unit 100 and the solid-liquid separation unit 200 can constitute an integrated device.
Some embodiments of the desulfurization method of the present invention, using the desulfurization apparatus shown in FIG. 1, include:the desulfurization reaction unit 100 receives a gas 300 to be treated containing sulfur dioxide and oxygen and introduces it into a desulfurization mixture 110, the desulfurization mixture 110 being mainly composed of water 112 and activated carbon catalyst particles 111, the ratio of the mass of the activated carbon catalyst particles 111 to the mass of the water 112 in the desulfurization mixture 110 being 0.05 to 1 and the specific surface area of the activated carbon catalyst particles 111 being not less than 500m2(ii)/g; sulfur dioxide and oxygen in the gas 300 to be treated are absorbed by the desulfurization mixture 110 and converted into sulfuric acid existing in the desulfurization mixture 110 when the gas 300 to be treated passes through the desulfurization mixture 110 in the desulfurization reaction unit 100, and the treated tail gas 320 is discharged from the desulfurization reaction unit 100, and the flow rate (m) of the gas to be treated passing through the desulfurization mixture 110 is controlled3H) volume of desulfurized mixture (m)3) The ratio of 400-4000h-1(ii) a The solid-liquid separation unit 200 receives the desulfurization mixture 110 reaching a certain sulfuric acid concentration output by the desulfurization reaction unit 100 and performs solid-liquid separation treatment on the desulfurization mixture 110 reaching the certain sulfuric acid concentration to obtain a sulfuric acid product 400 and activated carbon catalyst particles 111 serving as raw materials of a subsequent desulfurization mixture, respectively.
The technical concept of the above desulfurization method is based on the following desulfurization mechanism: because the desulfurization mixture is mainly composed of water and activated carbon catalyst particles, sulfur dioxide and oxygen in the gas to be treated are absorbed by the water when the gas passes through the desulfurization mixture to form a dissolved sulfur source and an oxygen source, and the sulfur source and the oxygen source react to generate sulfuric acid under the catalytic action of the activated carbon catalyst particles, so that desulfurization is realized. The desulfurization mechanism is obviously different from that of the traditional fixed bed activated carbon-based catalytic desulfurization technology in material, and the problem that the traditional fixed bed activated carbon-based catalytic desulfurization technology is H in H can be effectively solved2SO4The catalytic reaction rate rapidly decreases after the occurrence in the pores of the activated carbon catalyst. On the basis, the desulfurization method is configured by combining three key technical parameters of the mass ratio of the activated carbon catalyst particles to the mass of the water in the desulfurization mixture, the specific surface area of the activated carbon catalyst particles and the ratio of the gas flow to be treated passing through the desulfurization mixture to the volume of the desulfurization mixtureThe method can achieve higher desulfurization efficiency and other comprehensive benefits in practice.
Specifically, setting the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture to be 0.05 to 1 helps to dissolve sulfur dioxide and oxygen more sufficiently in water and to secure the catalytic reaction effect of the activated carbon catalyst particles on the dissolved sulfur source and oxygen source. When the mass ratio of the activated carbon catalyst particles to the water is less than 0.05, the content of the activated carbon catalyst particles is too low, the provided active sites are insufficient, and the catalytic reaction effect is poor; when the ratio of the mass of the activated carbon catalyst particles to the mass of water is greater than 1, the content of water is too low, which is not favorable for sufficient dissolution of sulfur dioxide and oxygen and is liable to cause the desulfurization mixture to be too viscous to facilitate the handling of the desulfurization mixture. The specific surface area of the activated carbon catalyst particles was set to 500m2Above the volume of the active carbon catalyst particles, on one hand, the basic active site requirement of the active carbon catalyst particles of unit mass is ensured, and on the other hand, the active carbon catalyst particles have active carbon catalyst morphology, which shows that the pores of the active carbon catalyst particles are fully exposed, and the influence of the internal diffusion of the active carbon catalyst is favorably eliminated. While the flow rate (m) of the gas to be treated which will pass through said desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio is controlled to 400-4000h-1And the desulfurization effect is further ensured by restricting the relationship between the flow of the gas to be treated and the volume of the desulfurization mixture. Flow rate (m) of gas to be treated while passing through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio of the water to the oil is less than 400h-1In time, the operating economy of the desulfurization process is poor; flow rate (m) of gas to be treated while passing through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio of the two is more than 4000h-1In the case of the conventional desulfurization method, the desulfurization effect is poor. In summary, the desulfurization method can be practically realized to achieve higher quality by the combined configuration of three key technical parameters, namely the mass ratio of the activated carbon catalyst particles to the mass of the water in the desulfurization mixture, the specific surface area of the activated carbon catalyst particles and the volume ratio of the gas flow to be treated passing through the desulfurization mixture to the volume of the desulfurization mixtureThe desulfurization efficiency and the economic efficiency of the desulfurization method can be better achieved.
It should be noted that, in the desulfurization method, the parameter related to the content of the substance in the desulfurization mixture, particularly the ratio of the mass of the activated carbon catalyst particles 111 to the mass of the water 112 in the desulfurization mixture 110, dynamically changes during the actual operation of the desulfurization method, but the "ratio of the mass of the activated carbon catalyst particles to the mass of the water 112 in the desulfurization mixture" defined in the present invention may refer to the ratio of the mass of the activated carbon catalyst particles 111 to the mass of the water 112 in the desulfurization mixture 110 at the beginning of the desulfurization method operation, or the ratio of the mass of the activated carbon catalyst particles 111 to the mass of the water 112 in the desulfurization mixture 110 during the desulfurization method operation. The specific surface area of the activated carbon catalyst particles 111 can be measured by separating the activated carbon catalyst particles 111 from the desulfurization mixture 110, washing and drying the particles sufficiently, and then detecting the particles.
In addition, sulfuric acid may be added to the desulfurization mixture 110 as a second dispersed phase at the beginning of the operation of the desulfurization method, so that the sulfuric acid concentration of the sulfuric acid solution in the desulfurization mixture 110 during the operation of the desulfurization method may be increased, and the sulfuric acid product obtained after the solid-liquid separation treatment may be utilized. The mass concentration of the sulfuric acid solution in the desulfurization mixture 110 can be controlled to be generally less than 35%, and particularly, the mass concentration of the sulfuric acid solution in the desulfurization mixture 110 at the beginning of the operation of the desulfurization method can be controlled to be 5 to 30%, more preferably 10 to 25%, and even more preferably 15 to 20%, so that the sulfuric acid concentration of the sulfuric acid product obtained after the solid-liquid separation treatment can be increased while the desulfurization efficiency is ensured.
The above desulfurization methods will be carried out by the following experimental examples, respectively. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
First, referring to fig. 2, the basic experimental method of the following experimental examples is: weighing a certain amount of the powder, grinding and sievingThe activated carbon catalyst particles are placed in a desulfurization reactor 11 (a stirring bubbling reactor is adopted), a proper amount of water or sulfuric acid solution is added to prepare a desulfurization mixture, and the desulfurization reactor 11 is placed in a magnetically-stirred constant-temperature water bath 12. Regulating the flow rates of nitrogen, sulfur dioxide and oxygen to the required flow rates, and measuring the SO of the original simulated gas (i.e., the gas to be treated) by a flue gas analyzer 132And O2The concentration of (c). After the concentration measurement of the original simulation gas is stable, switching the three-way valve to lead all the gas to be introduced into the reactor, and measuring the SO at the outlet2And O2The data were recorded every 1 minute or every 5 minutes (volume percentage concentration). After the desulfurization experiment was completed, the desulfurization mixture in the reactor was centrifuged, 1ml of liquid was measured, and the sulfuric acid concentration was measured with a NaOH standard solution.
SO2Removal efficiency η was calculated using the following notations:
Figure BDA0002264234890000101
in the formula, CSO2Representing the sulfur dioxide concentration in volume percent.
Experimental example 1
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 75g of distilled water, stirring, and injecting activated carbon slurry (namely, desulfurization mixture, the same applies below) into the stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particles to water was 0.4. Introducing SO2The concentration was 0.2% (5714 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min, the oxygen content of 10.08 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration component, and the size of an air outlet of the microporous aeration component is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the two is about 800h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 3. The desulfurization efficiency of the stable stage is about 99 percent(ii) a The sulfuric acid concentration at the end of the experiment was 2.41%.
Experimental example 2
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 20% (mass concentration, the same below) sulfuric acid, stirring, and preparing activated carbon slurry to be injected into the stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.341, and the mass ratio of the activated carbon catalyst particle mass to water was 0.426. Introducing SO2The concentration was 0.194% (5543 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min and the oxygen content of 10.02 percent and the water vapor content of 5 percent is introduced into the stirring bubbling reactor through the microporous aeration part, and the size of an air outlet of the microporous aeration part is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 4. The desulfurization efficiency in the stabilization stage is about 97.4%; the sulfuric acid concentration after the end of the experiment was 22.5%.
Experimental example 3
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 90g of 30% sulfuric acid, stirring, and preparing activated carbon slurry, and injecting the activated carbon slurry into a stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.333, and the mass ratio of the activated carbon catalyst particle mass to water was 0.476. Introducing SO2The concentration was 0.194% (5543 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min, the oxygen content of 10.18 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration part, and the size of an air outlet of the microporous aeration part is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1Controlling the temperature of the slurry to be 50 ℃, testing the desulfurization performance of the slurry,the results are shown in FIG. 5. The desulfurization efficiency in the stabilization stage is about 89%; the sulfuric acid concentration after the completion of the experiment was 31.7%.
Experimental example 4
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 80g of 7.8% sulfuric acid, stirring, preparing activated carbon slurry, and injecting into a stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.375, and the mass ratio of the activated carbon catalyst particle mass to water was 0.407. Introducing SO2The concentration was 0.3005% (8585 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min, the oxygen content of 10.18 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration part, and the size of an air outlet of the microporous aeration part is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 6. The desulfurization efficiency in the stabilization stage is about 99.0 percent; the sulfuric acid concentration after the completion of the experiment was 10.44%.
Experimental example 5
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 21.9% sulfuric acid, stirring, and making into activated carbon slurry, and injecting into a stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.341, and the mass ratio of the activated carbon catalyst particle mass to water was 0.437. Introducing SO2The concentration was 0.2% (5714 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min, the oxygen content of 10.37 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration part, and the size of an air outlet of the microporous aeration part is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1Controlling the slurryThe desulfurization performance was measured at a temperature of 50 ℃ and the results are shown in FIG. 7. The desulfurization efficiency in the stabilization stage is about 97 percent; the sulfuric acid concentration after the completion of the experiment was 24.3%.
Experimental example 6
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 24.3% sulfuric acid, stirring, and preparing activated carbon slurry to be injected into the stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.341, and the mass ratio of the activated carbon catalyst particle mass to water was 0.45. Introducing SO2The concentration was 0.192% (5486 mg/Nm)3) The simulated gas to be treated with the oxygen content of 15.01 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration component, and the size of an air outlet of the microporous aeration component is about 1 millimeter. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 8. The desulfurization efficiency in the stabilization stage is about 97.4%; the sulfuric acid concentration after the completion of the experiment was 26.6%.
Experimental example 7
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 10% sulfuric acid, stirring, and preparing activated carbon slurry to be injected into the stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.341, and the mass ratio of the activated carbon catalyst particle mass to water was 0.379. Introducing SO2The concentration was 0.192% (5486 mg/Nm)3) The simulated gas to be treated with the oxygen content of 10.39 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration component, and the size of an air outlet of the microporous aeration component is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) Ratio of (A to B)About 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 30 ℃ and the results are shown in FIG. 9. The desulfurization efficiency of the stabilization stage is about 99 percent; the sulfuric acid concentration after the completion of the experiment was 12%.
Experimental example 8
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 12% sulfuric acid, stirring, and preparing activated carbon slurry to be injected into a stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.341, and the mass ratio of the activated carbon catalyst particle mass to water was 0.387. Introducing SO2The concentration was 0.203% (5800 mg/Nm)3) The simulated gas to be treated with the oxygen content of 10.28 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration component, and the size of an air outlet of the microporous aeration component is about 1 millimeter. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 80 ℃ and the results are shown in FIG. 10. The desulfurization efficiency of the stabilization phase is about 100 percent; the sulfuric acid concentration after the end of the experiment was 15%.
Experimental example 9
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 10% sulfuric acid, stirring, and preparing activated carbon slurry to be injected into the stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particle mass to the sulfuric acid solution was 0.341, and the mass ratio of the activated carbon catalyst particle mass to water was 0.379. Introducing SO2The concentration was 0.076% (2171 mg/Nm)3) The simulated gas to be treated with the oxygen content of 9.83 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration component, and the size of an air outlet of the microporous aeration component is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) mixing with desulfurizationVolume of composition (m)3) The ratio of the two is about 1500h-1The desulfurization performance was measured by controlling the temperature of the slurry to 80 ℃ and the results are shown in FIG. 11. The desulfurization efficiency of the stabilization stage is about 91 percent; the sulfuric acid concentration after the end of the experiment was 11.8%.
Experimental example 10
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 80g of water, stirring, preparing activated carbon slurry, and injecting the activated carbon slurry into a stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particles to the water was 0.375, and SO was introduced2The concentration was 0.20% (5714 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min, the oxygen content of 10.19 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration part, and the size of an air outlet of the microporous aeration part is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 12. After 42h of desulfurization, the efficiency is still higher than 95%; the sulfuric acid concentration after the completion of the experiment was 21.9%.
Experimental example 11
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 103g of 40% sulfuric acid, stirring, and preparing activated carbon slurry, and injecting into a stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particles to water was 0.485. Introducing SO2The concentration was 0.193% (5514 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min, the oxygen content of 10.07 percent, the water vapor content of 5 percent and the flow rate of 1L/min is introduced into the stirring bubbling reactor through the microporous aeration component, and the size of an air outlet of the microporous aeration component is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The temperature of the slurry was controlled to 50 ℃ and the desulfurization was measuredThe results of the performance are shown in FIG. 13. The desulfurization efficiency in the stabilization phase is about 34.5%; the sulfuric acid concentration after the completion of the experiment was 40.9%.
Experimental example 12
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 20% sulfuric acid, stirring, and preparing activated carbon slurry to be injected into the stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particles to water was 0.426. Introducing SO2The concentration was 0.2026% (5789 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min and the oxygen content of 5.34 percent and the water vapor content of 5 percent is introduced into the stirring bubbling reactor through the microporous aeration part, and the size of an air outlet of the microporous aeration part is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 14. The desulfurization efficiency in the stabilization phase is about 78.1%; the sulfuric acid concentration after the completion of the experiment was 21.9%.
Experimental example 13
Grinding and sieving coal granular active carbon, weighing 30g active carbon catalyst granules with particle size less than 200 meshes (specific surface area of the active carbon catalyst granules is 830 m)2And/g), adding 88g of 20% sulfuric acid, stirring, and preparing activated carbon slurry to be injected into the stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particles to water was 0.426. Introducing SO2The concentration was 0.3036% (8674 mg/Nm)3) The simulated gas to be treated with the flow rate of 1L/min and the oxygen content of 5.09 percent and the water vapor content of 5 percent is introduced into the stirring bubbling reactor through the microporous aeration part, and the size of an air outlet of the microporous aeration part is about 1 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the first to the second is about 750h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 15. The desulfurization efficiency in the stabilization phase is about 59.1%; after the experiment is finishedThe sulfuric acid concentration was 21.9%.
Experimental example 14
Commercially available coal granular activated carbon is ground and sieved, 30g of activated carbon catalyst particles with the particle size of less than 200 meshes (the specific surface area of the activated carbon catalyst particles is 830m2/g) are weighed, 75g of distilled water is added into the particles and then stirred, and activated carbon slurry (namely a desulfurization mixture, the same applies below) is prepared and injected into a stirring bubbling reactor. At this time, the mass ratio of the activated carbon catalyst particles to water was 0.4. A gas to be treated simulated, which had a concentration of SO2 of 0.208% (5714mg/Nm3), an oxygen content of 10.31%, a water vapor content of 5%, and a flow rate of 1L/min, was introduced into the stirred bubble reactor through the micro-porous aeration section, but the size of the gas outlet of the micro-porous aeration section was increased to 2 mm. At this time, the flow rate (m) of the gas to be treated3H) volume of desulfurized mixture (m)3) The ratio of the two is about 800h-1The desulfurization performance was measured by controlling the temperature of the slurry to 50 ℃ and the results are shown in FIG. 16. The desulfurization efficiency in the stabilization phase is about 84.9%; the sulfuric acid concentration at the end of the experiment was 1.4%.
For comparison, the relevant parameters of the above experimental examples 1 to 14 are shown in Table 1 (see the following page). The "particle diameter less than 200 mesh" described in the above experimental examples 1 to 14 and "< 200 mesh" correspondingly recorded in table 1 mean that the particles of the activated carbon catalyst weighed were all passed through a 200 mesh sieve.
TABLE 1
Figure BDA0002264234890000151
Figure BDA0002264234890000161
As can be seen from the above-mentioned experimental examples 1 to 14 and the cases listed in Table 1, the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture is preferably in the range of 0.1 to 0.6, for example, 0.2, 0.3, 0.4, 0.5, etc. Of course, the ratio of the mass of activated carbon catalyst particles to the mass of water in the desulfurization mixture may also be less than 0.1, such as 0.05, 0.06, 0.07, 0.08, or 0.09,at this time, considering that the content of the activated carbon catalyst particles is low, it is considered to use activated carbon catalyst particles having a larger specific surface area and/or the flow rate (m) of the gas to be treated to pass through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio is set lower to ensure a certain desulfurization efficiency. The ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture may also be higher than 0.5, for example up to 0.7, 0.8, 0.9 or 1, in which case it is possible to envisage using activated carbon catalyst particles having a smaller specific surface area and/or the flow rate (m) of the gas to be treated which will pass through said desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio is set higher.
As can be seen from the above-mentioned experimental examples 1 to 14 and the cases listed in Table 1, the oxygen content of the gas to be treated is generally 5% by volume or more, preferably 10% by volume or more.
The temperature of the desulphurisation mixture also has some influence on the desulphurisation. Low temperature of the desulfurization mixture favors SO2And O2Do not favour the dissolved SO2With dissolved O2The reaction of (1). The temperature of the devulcanization mixture is most preferably 40-60 degrees celsius.
In addition, the introduction of the gas to be treated, particularly oxygen therein, into the desulfurization mixture by means of aeration using the microporous aeration member in the desulfurization mixture can significantly improve the desulfurization efficiency. The size of the air outlet of the microporous aeration member is preferably 1 mm or less, more preferably 700 micrometers or less, 500 micrometers or less, or 100 micrometers or less.
From the above experimental examples in combination with the inventors' experience, it can be determined that the flow rate (m) of the gas to be treated passes through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio of the first to the second may be 400-4000h-1. Flow rate (m) of gas to be treated while passing through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio of the water to the oil is less than 400h-1In time, the desulfurization process is less economical to operate (the desulfurization reaction unit needs to be particularly bulky); flow rate (m) of gas to be treated while passing through the desulfurization mixture3Volume of mixture of/h) and desulfurization(m3) The ratio of the two is more than 4000h-1In the case of the conventional desulfurization method, the desulfurization effect is poor.
According to the above experimental examples, it can be further found that: flow rate (m) of gas to be treated through the desulfurization mixture3H) volume of desulfurized mixture (m)3) The ratio is usually set to 500-2000h-1It is preferable.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. Based on the above disclosure of the present invention, all other preferred embodiments and examples obtained by a person skilled in the art without any inventive step should fall within the scope of protection of the present invention.

Claims (32)

1. A method of desulfurization, comprising:
the desulfurization reaction unit receives a gas to be treated comprising sulfur dioxide and oxygen and introduces it into a desulfurization mixture consisting essentially of water and activated carbon catalyst particles, the ratio of the mass of the activated carbon catalyst particles to the mass of the water in the desulfurization mixture being 0.05 to 1 and the specific surface area of the activated carbon catalyst particles being not less than 500m2/g；
Sulfur dioxide and oxygen in the gas to be treated are absorbed by the desulfurization mixture and converted into sulfuric acid existing in the desulfurization mixture when the gas to be treated passes through the desulfurization mixture in the desulfurization reaction unit, the treated tail gas is discharged from the desulfurization reaction unit, and the flow rate (m) of the gas to be treated passing through the desulfurization mixture is controlled3H) volume of desulfurized mixture (m)3) The ratio of 400-4000h-1；
The solid-liquid separation unit receives the desulfurization mixture which is output by the desulfurization reaction unit and reaches a certain sulfuric acid concentration, and carries out solid-liquid separation treatment on the desulfurization mixture which reaches the certain sulfuric acid concentration, so as to respectively obtain a sulfuric acid product and activated carbon catalyst particles which are used as raw materials of subsequent desulfurization mixtures.
2. The desulfurization method according to claim 1, characterized in that: at least a portion of the oxygen and the sulfur dioxide are both native to the source of the gas to be treated.
3. The desulfurization method according to claim 1 or 2, characterized in that: the volume percentage content of oxygen in the gas to be treated is not less than 3%, preferably more than 5%, and more preferably more than 10%.
4. The desulfurization method according to claim 1 or 2, characterized in that: the sulfur dioxide content of the gas to be treated is not higher than 3% by volume, preferably not higher than 1% by volume, and more preferably not higher than 0.5% by volume.
5. The desulfurization method according to claim 1 or 2, characterized in that: the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture is 0.1 to 0.6.
6. The desulfurization method according to claim 1 or 2, characterized in that: the temperature of the desulfurization mixture in the desulfurization reaction unit is 20-90 ℃, preferably 30-80 ℃, and more preferably 40-60 ℃.
7. The desulfurization method according to claim 1 or 2, characterized in that: the particle size of the activated carbon catalyst particles is between the requirements of ensuring that all activated carbon catalyst particles pass through a 10-mesh or 50-mesh screen and ensuring that all activated carbon catalyst particles pass through a 2000-mesh or 1000-mesh screen.
8. The desulfurization method according to claim 1 or 2, characterized in that: the solid-liquid separation unit adopts any one of a cyclone separator, a centrifugal filter, a plate-and-frame filter press, a membrane filter and a natural settling tank.
9. The desulfurization method according to claim 1 or 2, characterized in that: the active carbon catalyst particles are prepared by grinding at least one of coal active carbon, biomass active carbon, modified active carbon, a flue gas desulfurization catalyst taking the active carbon as a carrier, a waste active carbon desulfurizer obtained after fixed bed active carbon-based catalytic desulfurization and active carbon fibers.
10. The desulfurization method according to claim 1 or 2, characterized in that: the gas to be treated is introduced into the desulfurization mixture with the stirring operation of the desulfurization mixture; and/or the like and/or,
the gas to be treated and/or the oxygen make-up gas stream that is part of the gas to be treated are introduced into the desulfurization mixture by means of aeration in the desulfurization mixture.
11. The desulfurization method of claim 10, wherein: the aeration disperses the gas to be aerated in the desulfurization mixture through the microporous aeration part, and the size of the air outlet of the microporous aeration part is less than 3 mm, less than 1 mm or less than 500 microns.
12. The desulfurization method of claim 10, wherein: the desulfurization reaction unit adopts any one of a spray stirring reactor, a bubbling stirring reactor, a jet bubbling reactor, a stirring turbulent ball reactor and a sieve plate tower.
13. A desulfurization process characterized by comprising the following that occurs in a desulfurization reaction unit:
receiving a gas to be treated containing sulfur dioxide and oxygen and introducing them into a desulfurization mixture;
absorbing sulfur dioxide and oxygen by water serving as a continuous phase in the desulfurization mixture and forming a dissolved sulfur source and an oxygen source;
the active carbon catalyst particles serving as a dispersed phase in the desulfurization mixture enable a sulfur source and an oxygen source on the surface of the dispersed phase to generate sulfuric acid;
and discharging the tail gas treated from the desulfurization mixture.
14. The desulfurization method of claim 13, wherein: at least a portion of the oxygen and the sulfur dioxide are both native to the source of the gas to be treated.
15. The desulfurization method according to claim 13 or 14, characterized in that: the volume percentage content of oxygen in the gas to be treated is not less than 3%, preferably more than 5%, and more preferably more than 10%.
16. The desulfurization method according to claim 13 or 14, characterized in that: the sulfur dioxide content of the gas to be treated is not higher than 3% by volume, preferably not higher than 1% by volume, and more preferably not higher than 0.5% by volume.
17. The desulfurization method according to claim 13 or 14, characterized in that: the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture is 0.05 to 1 and the specific surface area of the activated carbon catalyst particles is not less than 500m2(ii)/g; controlling the flow (m) of gas to be treated through the desulphurisation mixture3H) volume of desulfurized mixture (m)3) The ratio of 400-4000h-1。
18. The desulfurization method of claim 17, wherein: the ratio of the mass of the activated carbon catalyst particles to the mass of water in the desulfurization mixture is 0.1 to 0.6.
19. The desulfurization method according to claim 13 or 14, characterized in that: the method is characterized in that: the temperature of the desulfurization mixture in the desulfurization reaction unit is 20-90 ℃, preferably 30-80 ℃, and more preferably 40-60 ℃.
20. The desulfurization method according to claim 13 or 14, characterized in that: the particle size of the activated carbon catalyst particles is between the requirements of ensuring that all activated carbon catalyst particles pass through a 10-mesh or 50-mesh screen and ensuring that all activated carbon catalyst particles pass through a 2000-mesh or 1000-mesh screen.
21. The desulfurization method according to claim 13 or 14, characterized in that: the active carbon catalyst particles are prepared by grinding at least one of coal active carbon, biomass active carbon, modified active carbon, a flue gas desulfurization catalyst taking the active carbon as a carrier, a waste active carbon desulfurizer obtained after fixed bed active carbon-based catalytic desulfurization and active carbon fibers.
22. The desulfurization method according to claim 13 or 14, characterized in that: the gas to be treated is introduced into the desulfurization mixture with the stirring operation of the desulfurization mixture; and/or the like and/or,
the gas to be treated and/or the oxygen make-up gas stream that is part of the gas to be treated are introduced into the desulfurization mixture by means of aeration in the desulfurization mixture.
23. The desulfurization method of claim 22, wherein: the aeration disperses the gas to be aerated in the desulfurization mixture through the microporous aeration part, and the size of the air outlet of the microporous aeration part is less than 3 mm, less than 1 mm or less than 500 microns.
24. Desulfurization equipment, including desulfurization reaction unit, its characterized in that: the desulfurization reaction unit is a desulfurization reaction unit used in the desulfurization method according to any one of claims 13 to 21.
25. The desulfurization apparatus of claim 24, wherein: the desulfurization reaction unit comprises a stirring device which is used for stirring the desulfurization mixture along with the introduction of the gas to be treated into the desulfurization mixture; and/or the like and/or,
the desulfurization reaction unit comprises an aeration device which introduces the gas to be treated and/or an oxygen supplement gas flow which is a part of the gas to be treated into the desulfurization mixture in a manner of aeration in the desulfurization mixture.
26. The desulfurization apparatus of claim 25, wherein: the desulfurization reaction unit adopts any one of a spray stirring reactor, a bubbling stirring reactor, a jet bubbling reactor, a stirring turbulent ball reactor and a sieve plate tower.
27. The desulfurization method of claim 25, wherein: the aeration device comprises a micropore aeration component, and the size of an air outlet of the micropore aeration component is less than 3 mm, less than 1 mm or less than 500 microns.
28. A desulfurization mixture, comprising:
water as the continuous phase;
activated carbon catalyst particles as a dispersed phase;
wherein the ratio of the mass of the activated carbon catalyst particles to the mass of water is 0.05 to 1 and the specific surface area of the activated carbon catalyst particles is not less than 500m2/g。
29. The desulfurization mixture of claim 28, wherein: the ratio of the mass of the activated carbon catalyst particles to the mass of water is 0.1 to 0.6.
30. The desulfurization mixture of claim 28 or 29, wherein: the active carbon catalyst particles are prepared by grinding at least one of coal active carbon, biomass active carbon, modified active carbon, a flue gas desulfurization catalyst taking the active carbon as a carrier, a waste active carbon desulfurizer obtained after fixed bed active carbon-based catalytic desulfurization and active carbon fibers.
31. The desulfurization mixture of claim 28 or 29, wherein: the particle size of the activated carbon catalyst particles is between the requirements of ensuring that all activated carbon catalyst particles pass through a 10-mesh or 50-mesh screen and ensuring that all activated carbon catalyst particles pass through a 2000-mesh or 1000-mesh screen.
32. The desulfurization mixture of claim 28 or 29, wherein: the desulfurization mixture also comprises sulfuric acid as a second dispersed phase, and the mass concentration of the sulfuric acid in the sulfuric acid solution in the desulfurization mixture is below 40%; alternatively, the first and second electrodes may be,
sulfuric acid is also included as a second dispersed phase and the desulfurization mixture is the initial desulfurization mixture for the desulfurization process, the sulfuric acid solution in the desulfurization mixture having a sulfuric acid concentration of 5 to 30% by mass, more preferably 10 to 25% by mass, and still more preferably 15 to 20% by mass.
CN201911081907.4A 2019-10-22 2019-11-05 Desulfurization method, desulfurization apparatus, and desulfurization mixture Pending CN110947300A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1824372A (en) * 2006-01-23 2006-08-30 华东理工大学 Method of desulfurizing and denitrate simultaneously of exhaust gas by micro wave catalysis

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
CN1824372A (en) * 2006-01-23 2006-08-30 华东理工大学 Method of desulfurizing and denitrate simultaneously of exhaust gas by micro wave catalysis

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