CN113413723A - Method for treating waste gas by using ion exchange resin - Google Patents

Method for treating waste gas by using ion exchange resin Download PDF

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CN113413723A
CN113413723A CN202110787078.2A CN202110787078A CN113413723A CN 113413723 A CN113413723 A CN 113413723A CN 202110787078 A CN202110787078 A CN 202110787078A CN 113413723 A CN113413723 A CN 113413723A
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resin
ion exchange
oxidant
flue gas
exchange resin
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CN113413723B (en
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樊振江
史磊
杨斌
范瑞华
田二飞
李龙博
杨海岳
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Shenzhen Haoquan Environmental Protection Co ltd
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Shenzhen Qianhai Zhongsheng Environmental Protection Technology 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
    • B01D53/025—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 wetted adsorbents; Chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/57—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for anionic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/206—Ion exchange resins
    • 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
    • B01D2257/302—Sulfur oxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

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Abstract

The application relates to a method for treating waste gas by using ion exchange resin, which comprises the steps of flue gas pretreatment, resin oxidation, desulfurization and denitrification, and oxidant solution recycling, wherein an oxidant is used for converting common ion exchange resin into a form with an oxidizing group, so that the common ion exchange resin has an ion exchange function and strong oxidizing property, and the form of intermittently spraying a regenerant can realize the purposes of no shutdown, no production shutdown, oxidation, exchange and partial regeneration of the exchange resin and has high-efficiency desulfurization and denitrification performance.

Description

Method for treating waste gas by using ion exchange resin
Technical Field
The application relates to the technical field of flue gas desulfurization and denitration, relates to a method for treating waste gas by using ion exchange resin, and particularly relates to a method for purifying flue gas by using ion exchange resin and simultaneously performing partial regeneration on the flue gas.
Background
The industrial flue gas refers to flue gas and dust generated by combustion of an industrial boiler. Main pollution factors in flue gas of industrial boilers: sulfur dioxide (SO)2) Nitrogen Oxide (NO)x) And particulate matter, etc. are one of the main factors affecting the atmosphere environment, SO in flue gas2、NOxAnd particulate matters can not be stably discharged after reaching standards, and effective control of sulfur dioxide and nitrogen oxides in industrial flue gas is a main problem in the industry.
At present, most of small coal-fired boilers adopt a simple wet desulphurization and dust removal integrated technology, the dust removal efficiency is about 90%, the desulphurization efficiency is about 50% (low-sulfur fuel is completely used), and the denitration efficiency is less than 10%. The flue gas purification technology of large coal-fired boilers mainly comprises bag type dust removal, sodium-alkali method/calcium method desulfurization, selective catalytic reduction method denitration (SCR) and the like. The bag type dust collector has high dust collection efficiency which reaches 99.8%; the desulfurizer is automatically added into the desulfurization device, and the desulfurization efficiency reaches over 90 percent; when the SCR denitration device is put into operation, the denitration efficiency is over 50 percent, but the higher operation rate cannot be ensured due to the temperature window problem of the catalyst.
There is also a problem in that in the ion exchange resin regeneration process, since the adsorbed impurities are close to saturation after the ion exchange resin is used for a certain period of time, the regeneration treatment is required, and the ions and other impurities adsorbed by the resin are eluted and removed by using a chemical agent so as to restore the original composition and performance. However, in the regeneration process, shutdown is needed, the ion exchange resin is eluted and regenerated separately, the construction period is long, and the ion exchange resin needs to be used one by one. Meanwhile, in the whole desulfurization and denitrification process, the whole process needs to be shut down, the ion exchange resin is eluted and regenerated by a chemical reagent independently, time and labor are consumed, or standby equipment is adopted for operation, the investment is large, the production safety is possibly influenced, the process progress is reduced, and therefore negative effects in the aspects of economic loss and environmental protection in different degrees are brought.
Disclosure of Invention
In order to solve the technical problems, the application provides a method for simultaneously purifying, desulfurizing and denitrifying flue gas by using ion exchange resin and partially regenerating the ion exchange resin.
The application provides a method for regenerating an ion exchange resin material by intermittent spraying, which comprises the following specific steps: intermittently spraying oxidant solution, passing through the ion exchange resin layer at a certain flow rate, and partially regenerating the ion exchange resin;
the time interval of the intermittent spraying is 4-72 hours, the spraying time is 4-8 min/time, and the liquid spraying amount of the oxidant spraying solution is 1/4-1/6 resin volume dosage each time. The oxidant is K2Cr2O7、NaClO、Ca(ClO)2、NaClO2、H2O2、KMnO4One or more of (a).
The method for treating the waste gas by using the ion exchange resin comprises the following steps:
flue gas pretreatment, resin oxidation, desulfurization and denitrification, and regenerated liquid recycling.
Flue gas pretreatment: the treatment comprises the processes of dust removal and temperature reduction of the flue gas;
resin oxidation: intermittently spraying an oxidant solution, wherein the oxidant spraying solution passes through the resin layer at a certain flow rate to enable the ion exchange resin to become an oxidized ion exchange resin;
and (3) desulfurization and denitrification: SO2, NO in flue gasxOxidation product H of (2)2SO4、HNO3And H2SO3Meanwhile, the catalyst is adsorbed by ion exchange resin, so that the desulfurization and the denitrification are realized simultaneously;
and (3) recycling the solution: and (4) recycling the oxidant spraying solution, and recycling the regenerated waste liquid.
The flue gas pretreatment comprises the processes of dedusting and cooling the flue gas. The temperature of the flue gas discharged from a boiler is about 120-180 ℃, the adaptive temperature of ion exchange is below 60 ℃, and the temperature of the flue gas is reduced to 40-90 ℃, preferably 50-70 ℃ before the flue gas enters the ion exchange material, so that the ion exchange resin can reach the optimal use state during ion exchange, and the removal rate can be increased. Optionally, the pretreatment of the industrial flue gas also comprises dust removal treatment, and a large amount of dust particles in the industrial flue gas can block gaps in the resin layer and cover the anion exchange resin, so that the working exchange capacity of the ion exchange resin is reduced, and the desulfurization and denitrification effects in the subsequent process are easily reduced.
The flue gas cooling process can adopt a flue gas-water heat exchanger to reduce the temperature of the flue gas, and the heated water after absorbing the heat of the flue gas is conveyed back to the boiler for use, thereby greatly improving the thermal efficiency of the boiler. The method can reduce environmental pollution and protect the environment, and can also generate certain economic benefit. The energy-saving and environment-friendly effects are achieved. The flue gas cooling process can also adopt a flue gas cooling system, and the effect of cooling is also achieved.
According to at least one embodiment of the present application, the flue gas contains SO prior to pretreatment2 500～2000mg/m3The concentration of NO is 200-800 mg/m3The flue gas SO after being cooled by the flue gas heat exchanger and then treated2The emission concentration of NO and NO are both less than 35mg/m3。
The ion exchange resin is macroporous strong-base or weak-base anion exchange resin, and the anion exchange resin is preferably strong-base anion exchange resin.
The ion exchange resin may be selected from styrenic resins and acrylic resins.
According to at least one embodiment, the anion exchange resin is one containing functional groups including quaternary amine functional groups, secondary amine functional groups, primary amine functional groups, or tertiary amine functional groups.
The anion exchange resin is selected from the group consisting of a CO3 type strong base resin, an OH type strong base resin, and preferably an OH type strong base resin.
Specifically, one or more of commercially available D201SC resin, D309 resin, D301SC resin, D402 resin, SQD816 resin and SQD817 resin may be used.
In the resin oxidation process, oxidant with certain concentration is used for spraying solution, the solution passes through the resin layer at a certain flow rate, and anions of the ion exchange resin generate ion exchange reaction to enable the ion exchange resin to be in an oxidant form, so that the ion exchange resin has ion exchange and oxidation effects at the same time.
The oxidant is K2Cr2O7、NaClO、Ca(ClO)2、NaClO2、H2O2、KMnO4And the like.
Compared with a gas oxidant, the liquid oxidant solution is preferably selected, the liquid oxidant with the appropriate concentration is prepared, the spraying mode is adopted, the oxidation and ion exchange efficiency can be improved, the spraying operation is simple, the cost is low, the operation condition is simple and easy to control, and the production cost is reduced.
The application utilizes the basic principle of ion exchange to change the form of the exchange group of the ion exchange resin, SO that the ion exchange resin is used as an oxidant with the effect of a strong oxidant and is also used as an ion exchanger with the ion exchange function, and when smoke passes through the resin layer, SO in the smoke has the ion exchange function2And NO is firstly oxidized into nitrogen dioxide, dinitrogen pentoxide and sulfur trioxide which are easily dissolved in water, and then the nitrogen dioxide, the dinitrogen pentoxide and the sulfur trioxide are adsorbed by ion exchange resin, so that the aim of simultaneously desulfurizing and denitrifying is fulfilled.
According to at least one embodiment, the strong base anion exchange resin has a strong base anion exchange group (-CH)2N-(CH3)3Cl-) The exchangeable ions on the exchange groups of the common strong base anion exchange resin are chloride ions and have no oxidability. The structural formula is as follows:
Figure BDA0003159424810000031
when a liquid oxidant solution with a certain concentration, such as NaClO solution, is passed through the resin layer at a certain flow rate, the ClO in the solution-I.e. substituted Cl-Transformation of part of the resin to RClO:
RCl+NaClO→RClO+NaCl
the structural formula of RClO is as follows:
Figure BDA0003159424810000041
ClO adsorbed on resin-Is unstable and still has the function of a strong oxidant. The transformed ion exchange resin has thus become the oxidant form.
According to actual needs, a small amount of alkali solution (for example, 1 wt%) is added into the liquid oxidant solution to adjust the pH value of the system. NaClO is extremely strong in oxidizability under an acidic condition (PH5-6), the oxidizability of NaClO is quickly depleted, and the oxidation duration is short; although the oxidation property is slightly weakened under the alkaline condition (pH9-12), the oxidation property can be maintained for a longer time, so that in order to properly prolong the oxidation time of NaClO and reduce unnecessary consumption, a proper amount of alkali liquor is added to adjust the pH of the solution.
RCl+NaOH→ROH+NaCl
The alkali can be NaOH, KOH, NaHCO3,Na2CO3And one or more of ammonia water.
In the oxidant spraying solution, the content of the oxidant is 0.3-4 wt%, the content of the alkali liquor is 1-6 wt% and the balance is water, based on 100% of the solution.
Preferably, the oxidant spraying solution of the present application has an oxidant content of 0.5-3 wt% and an alkali solution content of 1-4 wt%.
The method adopts a mode of intermittently spraying the liquid oxidant solution, the specific spraying interval time is 4-72 hours, preferably 4-36 hours, and the solution spraying time is 4-8 min/time.
The liquid spraying amount of the oxidant spraying solution is 1/4-1/6 resin volume dosage each time.
According to the actual working condition, if SO is in the flue gas2,NOxThe time interval of spraying can be properly reduced when the concentration is higher and the ion exchange resin material needs to be regenerated in time, for example, 4 to 8 hours for ion exchangeAnd (4) carrying out spray regeneration on the resin material. If SO is in the flue gas2,NOxThe concentration is lower, and the spraying time interval can be properly prolonged, such as 1-3 days for spraying and regenerating the resin.
The resin oxidation process comprises: oxidation reaction and hydration reaction of the flue gas.
The oxidation reaction comprises a liquid oxidation reaction and a solid oxidation reaction process.
The liquid oxidation reaction refers to SO in the flue gas after the flue gas enters the ion exchange layer2NO and liquid NaClO carried on the surface of the ion exchange resin and in the gap are firstly subjected to oxidation reaction, and SO in the flue gas is obtained after oxidation2And NO is oxidized to form water-soluble SO3And NO2(ii) a The reaction equation is as follows:
Figure BDA0003159424810000051
Figure BDA0003159424810000052
the solid oxidation reaction refers to the unreacted SO in the flue gas after the flue gas enters the ion exchange resin layer2And NO continues to perform oxidation reaction with the ion exchange resin (RClO) which becomes the solid oxidant, and SO in the flue gas after oxidation2And NO is oxidized to SO3、NO2And N2O5；
Figure BDA0003159424810000053
Figure BDA0003159424810000054
Figure BDA0003159424810000055
The ion exchange resin after redox reaction is restored to chlorine type (RCl) and still has ion exchange capacity.
The hydration reaction refers to SO generated after oxidation3、NO2And N2O5Quickly dissolved in water to become H2SO4And HNO3Part of the SO not oxidized2Also generates H by hydration reaction with the aqueous solution in the resin layer2SO3。
Figure BDA0003159424810000056
Figure BDA0003159424810000057
Figure BDA0003159424810000058
Figure BDA0003159424810000059
The ion exchange reaction refers to H generated after oxidation and hydration reaction2SO4、HNO3And H2SO3And meanwhile, the catalyst is adsorbed by ion exchange resin, so that the aim of simultaneously desulfurizing and denitrifying is fulfilled.
Figure BDA00031594248100000510
Figure BDA0003159424810000061
Figure BDA0003159424810000062
Figure BDA0003159424810000063
Figure BDA0003159424810000064
Figure BDA0003159424810000065
Figure BDA0003159424810000066
After the ion exchange resin runs for a long time, NaClO contained in the pores of the resin and ClO adsorbed on the exchange groups of the resin-The decomposition gradually occurs, causing unnecessary loss, and the oxidizing agent may also be decomposed by itself. Therefore, the partial ion exchange resin is regenerated in time, unnecessary loss of strong oxidant is avoided, the intermittent spraying of the application can regenerate the resin in time, the problems are well solved, and the turnover rate and the utilization rate of the ion exchange resin are improved
When the flue gas discharges SO2When the concentration of NO exceeds the standard, indicating that the ClO is on the resin-When depleted, the oxidizing power has been lost and regeneration is required.
The intermittent spraying mode of spraying the solution by controlling the oxidant can adjust the spraying time, the interval time and the frequency, and can realize the partial regeneration function of the resin at the same time.
Taking oxidant solution NaClO + NaOH as an example, when the spraying solution passes through the resin layer, part of the resin is changed into RClO type again, and SO can be continuously oxidized2And NO. The basic principle is as follows:
Figure BDA0003159424810000067
Figure BDA0003159424810000068
Figure BDA0003159424810000069
Figure BDA00031594248100000610
Figure BDA00031594248100000611
Figure BDA00031594248100000612
in the conventional ion exchange process, the ion exchange process is to remove some ions, and the regeneration process is to elute some ions adsorbed on the resin by using a regenerant, so that the exchange and regeneration are completely opposite processes, and cannot be performed simultaneously.
In the application, the liquid oxidant solution is intermittently sprayed, so that the regeneration and the exchange of the resin can be simultaneously carried out. Because the oxidant is also a regenerant at the same time, the oxidant can be used for treating SO in the flue gas2And NO has strong oxidizing effect, and when the oxidizing agent and the flue gas simultaneously pass through the resin layer, the liquid oxidizing agent can react with SO in the flue gas2And NO undergoes redox reactions. Specifically, when an oxidizing agent (i.e., a regenerant) and flue gas enter the resin bed simultaneously, the resin first adsorbs anions such as ClO in the liquid oxidizing agent because the concentration of the oxidizing agent is nearly ten thousand times different from the concentration of SO and NO in the flue gas-RClO resin is formed to realize partial regeneration of the resin, and the regenerated resin can react with SO in the flue gas2Has oxidation and ion exchange functions with NO, and can regenerate ion exchange resin and simultaneously treat SO in flue gas2And NO undergoes oxidationAnd (4) carrying out primary reaction. (taking NaClO as an example):
NaClO+NO→NaCl+NO2
NaClO+2NO2→NaCl+N2O5
NaClO+SO2→NaCl+SO3
in the conventional desulfurization and denitrification process, the ion exchange resin fails in long-term operation, the ion exchange resin needs to be integrally stopped, the ion exchange resin is independently replaced or regenerated, the operation period and the operation cost are influenced by the stop of the operation, and the regeneration period generally needs 15 to 20 days.
The regeneration of the resin part is realized by spraying the oxidant, and the oxidation performance and the ion exchange performance are simultaneously achieved, so that the method is a great breakthrough in the current desulfurization and denitrification process, can realize the regeneration of the ion resin part in one day, and has high turnover rate and utilization rate of the ion exchange resin; not only the construction period is saved, the production is uninterrupted, but also the operation cost can be greatly reduced, the investment and the occupied area of standby equipment are reduced, the regeneration process is simplified, the resin utilization rate is improved, the using amount of the resin is reduced, the routine of shutdown regeneration is broken, the confusion that the equipment needs to be used one by one during the shutdown regeneration in the continuous operation is avoided, and the one-time investment is saved.
In addition, because the liquid oxidant probably has the problem of decomposing by oneself, if whole regeneration, it reaches 80% to need ion exchange resin rate of utilization/saturation volume, and the time is overlength, and ion exchange SOx/NOx control ability weakens, and the ion resin utilization ratio is low, and consequently, this application can in time realize resin part regeneration in one day through the mode that the intermittent type sprayed, can not wait that resin is all saturated, has improved the utilization ratio and the turnover rate of resin.
According to at least one embodiment, the partial regeneration of the resins of the present application consumes only half of the oxidant as the total regeneration of the resin (conventional shut-down, regeneration process), greatly reducing operating costs.
In addition, the desulfurization and denitrification process can be further based onUse of resin, flue gas SO2Adjusting the spraying interval period according to the conditions of NO concentration, desulfurization and denitrification effects and the like, and performing spraying regeneration on the ion exchange resin, such as SO in flue gas2,NOxUnder the condition of higher concentration, the spraying interval is shorter for 4-8 hours; SO in flue gas2,NOxIn the case of low concentration, the spraying time interval is longer, for example, 1 to 3 days, the resin is sprayed and regenerated.
According to at least one embodiment, the configured oxidant solution is fed into the water distribution system of the ion exchange device to regenerate and convert the ion exchange material. The oxidant spray solution was sprayed every 4 hours for 6 minutes each time.
In summary, in the intermittent spraying process of the present application, the oxidant spraying solution can simultaneously generate six reactions, SO, in the ion exchange layer2Mention is made of representative ions:
(1) liquid oxidation reaction
SO in flue gas2Firstly, carrying out oxidation reaction with liquid NaClO carried on the surface of the ion exchange material and in the gap:
Figure BDA0003159424810000081
(2) solid state oxidation reaction of resin
Unreacted SO in flue gas2Continuing the oxidation reaction with the ion exchange material (RClO) which has become the "solid oxidant":
Figure BDA0003159424810000082
(3) absorption reaction of alkali liquor
The leaching solution contains a small amount of NaOH and residual SO2Is easily absorbed by NaOH carried on the surface of the ion exchange material and in the gaps:
Figure BDA0003159424810000083
(4) hydration reactions
SO formed after oxidation3Quickly dissolved in water to become H2SO4：
Figure BDA0003159424810000084
(5) Ion exchange reaction
Generation of H2SO4Adsorption by ion exchange resin:
Figure BDA0003159424810000085
(6) part of the ion exchange resin was regenerated and converted to RClO form:
Figure BDA0003159424810000086
the solution recycling means that the oxidant spraying solution is recycled, the regenerated waste liquid is recycled, and the oxidant is prepared again for spraying. After the leaching solution passes through the resin layer, the leaching solution is equivalent to regenerating part of the resin, and the discharged regeneration waste solution contains a large amount of sulfate, sulfite and nitrate (Na)2SO4、Na2SO3And NaNO3) In order to save water and reduce the discharge amount of waste water, the discharged waste liquid passes through an ROH type ion exchange column, and a large amount of Na is added2SO4、Na2SO3And NaNO3And adsorbing the alkaline solution on the resin, and completely recovering the treated alkaline solution for preparing the oxidant spraying solution again.
2ROH+Na2SO4→R2SO4+2NaOH
2ROH+Na2SO3→R2SO3+2NaOH
ROH+NaNO3→RNO3+NaOH
In the process, if the ROH strong base type ion exchange column is saturated and needs to be regenerated, the ion exchange column can be regenerated;
when the ROH strong base type ion exchange column is saturated, NaOH solution with a certain concentration and with a volume twice that of the resin is used for regeneration, the former time of regenerated waste liquid is discharged, and the latter time of regenerated waste liquid is reserved for recycling in the next regeneration.
R2SO4+2NaOH→2ROH+Na2SO4
R2SO3+2NaOH→2ROH+Na2SO3
RNO3+NaOH→ROH+NaNO3
The technical route characteristics and beneficial effect of this application do:
1. the method utilizes the spraying oxidant solution to convert the common ion exchange resin into a form with an oxidizing group, so that the common ion exchange resin has both an ion exchange function and strong oxidizing property.
2. This application is at ion exchange resin SOx/NOx control operation in-process, and equipment need not to shut down and carry out the transformation and the regeneration of resin simultaneously, has broken the regenerated convention of shutting down, has avoided the continuous operation equipment shut down regeneration need "one is equipped with one and uses" the puzzlement, has practiced thrift the disposable investment, realizes resin part regeneration in one day, has improved ion exchange resin's utilization ratio and turnover efficiency.
3. In the operation process of the equipment, the partial ion exchange resin is regenerated in time, the utilization rate of the resin is improved, the use amount of the resin and the oxidant is greatly reduced, and the experimental data verifies that the regeneration agent consumption of the partial regeneration of the resin is only less than half of the whole regeneration of the resin, so that the operation cost is greatly reduced.
4. This application sprays the form of oxidant solution through the intermittent type, can accomplish not stop work, not stop production, satisfy exchange resin oxidation, exchange, palingenetic integration simultaneously, and under the saturated condition of resin exchange, the intermittent type sprays oxidant solution and can realize resin part regeneration to have oxidation performance and ion exchange performance concurrently simultaneously, have efficient SOx/NOx control performance.
5. The process is suitable for treating low-temperature flue gas, the low-temperature flue gas generated by the production process does not need to be heated (a large amount of heat energy is consumed), and the low-temperature flue gas directly enters an ion exchange device to achieve double-low-concentration emission; the waste heat of high-temperature flue gas discharged by the production process can be recycled through the flue gas heat exchanger, and part of energy can be saved.
6. This application adopts ion exchange resin SOx/NOx control, sprays liquid through preparing suitable oxidant, not only can reach desulfurization efficiency 99.5%, denitration efficiency 98% above technological effect, can also spray the oxidant through control intermittent type and realize partial resin regeneration, improves the availability factor of resin.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the application and together with the description serve to explain the principles of the application.
FIG. 1 is a process flow diagram of example 1
Wherein 101-a liquid leaching tank, 102-a main desulfurization and denitrification device, 103-an ion exchange column, 104-a regenerated liquid recycling tank, 105-a regenerated liquid preparation tank, 106-a pH monitor, an ORP monitor and a TDS monitor
Detailed Description
The present application will be described in further detail with reference to the accompanying drawings and embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present application. It should be noted that, for convenience of description, only the portions related to the present application are shown in the drawings.
In addition, the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present disclosure will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
Example 1
To process 10000m3The desulfurization and denitrification process flow comprises the following steps:
1. flue gas pretreatment: flue gas containing SO2The concentration is 500-2000 mg/m3The concentration of NO is 200-800 mg/m3Starting the induced draft fan, cooling the flue gas by the flue gas heat exchanger to 10000m3Flow rate of/h passes through the main body equipment, and treated flue gas SO2The emission concentration of NO and NO are both less than 35mg/m3。
2. Spraying an oxidant solution: the spray oxidizer solution had a composition of 2.5% NaClO + 1% NaOH.
Preparing an oxidant solution with a diameter of about 3.5m in advance in a liquid spraying pool3(ii) a In the operation process of the main equipment, the pump 1 and the valve 1 are started to control the flow of the drenching liquid to be 16m3Perh (flow rate is about 2 times of volume of D201SC anion exchange resin, liquid pouring time is about 6 minutes, and liquid pouring amount is 1.6m in total3Equivalent to 0.2 times of the volume of the resin) and then the pump 1 and the valve 1 are closed. At this time, ClO in the shower liquid-I.e. replacing Cl on the resin exchange group1-Transformation of the resin to RClO, ClO adsorbed on the resin-Is unstable and still has the function of a strong oxidant. The transformed ion exchange resin has thus become a strong oxidant. When containing SO2ClO adsorbed on the resin exchange group when the flue gas with NO passes through the resin layer-I.e. SO in the flue gas2SO generated after oxidation by redox reaction with NO3、NO2And N2O5Quickly dissolved in water to become H2SO4And HNO3Part of the SO not oxidized2Also generates H by hydration reaction with the aqueous solution in the resin layer2SO3。
The ion exchange resin after redox reaction is restored to chlorine type (RCl) and still has ion exchange capacity. H in the resin layer2SO3、H2SO4And HNO3Is absorbed by ion exchange resin, thus achieving the aim of desulfurization and denitrification.
After 4 hours, the pump 1 and the valve 1 are turned on again, the oxidant solution is intermittently sprayed (the flow rate is about 2 times the volume of the resin, the spraying time is about 6 minutes), and anions in the oxidant such as ClO-react with the ion exchange resin to form an RClO treeThe resin can realize partial regeneration of the resin, and the regenerated resin can be used for treating SO in the flue gas2Has oxidation and ion exchange functions with NO, and can regenerate ion exchange resin and simultaneously treat SO in flue gas2And NO undergo redox reactions.
3. And (3) recycling the leaching solution: in order to fully utilize the oxidant and the alkali liquor in the leaching solution and further reduce the operation cost, the leaching solution in the actual production needs to be recycled for many times. The volume of the bottom box body of the main body equipment is about 5m3When the liquid level at the bottom of the main body equipment rises to a set position (a transparent liquid level meter is observed or liquid level automatic control is adopted), the pump 2 and the valve 2 are started, waste liquid is pumped into the liquid sprinkling pool, and new liquid sprinkling is configured according to the display numerical values of PH, ORP and TDS (accurate chemical dosing is achieved, and cost is saved). When the accumulated liquid at the bottom of the main body equipment is reduced to a set position, the pump 2 and the valve 2 are closed.
4. Liquid spraying and purification: in order to save water and reduce the discharge amount of waste liquid. After the leachate is reused for 10 times, the leachate needs to be purified according to the TDS display value. The pump 2, the valve 3 and the valve 4 are opened to control the flow 2m3And h, pumping the purified liquid into a liquid leaching pool, and preparing new leaching liquid according to the display numerical values of PH, ORP and TDS. When the accumulated liquid at the bottom of the main body equipment is reduced to a set position (a transparent liquid level meter is observed or liquid level automatic control is adopted), the pump 2, the valve 3 and the valve 4 are closed.
5. Regeneration of the exchange column: when the drenching liquid is purified and recovered by about 10m3On the left and right sides, the exchange column needs to be regenerated once, and during regeneration, the recovery liquid in the recovery tank is used for regeneration. The pump 3, the valve 7, the valve 9 and the valve 5 are started to control the flow rate to be 1m3H, 0.5m of regenerated waste liquid3Discharging, opening the valve 8 and the valve 6 after the regeneration recycling liquid is used up, closing the valve 5, pumping the regeneration liquid into a regeneration liquid recycling pool, closing the pump 3, the valve 9 and the valve 6 when the prepared regeneration liquid is used up, and after the regeneration is finished, the exchange column is used for standby.
Example 2
Spray oxidizer solution composition of 2% Ca (ClO)2+ 1% NaOH, the other steps are the same as in example 1.
Example 3
The spraying oxidant solution comprises the following components: 1.2% NaClO2+ 1% NaOH, the other steps are the same as in example 1.
Example 4
The conditions for treating the flue gas varied, and the oxidizing agent and other steps were the same as in example 1.
Example 5
The spraying oxidant solution consists of 2 percent of NaClO and 2 percent of NaHCO3The other steps are the same as in example 1.
Example 6
The spraying oxidant solution has the composition of 3.5 percent of KMnO4+ 2% NaOH, the other steps are the same as in example 1.
Example 7
The composition of the oxidant solution sprayed is 0.5% H2O2+ 2% NaOH, the other steps are the same as in example 1.
Comparative example 1
1. Flue gas pretreatment: flue gas containing SO2The concentration is 500-2000 mg/m3The concentration of NO is 200-800 mg/m3Starting the induced draft fan, cooling the flue gas by the flue gas heat exchanger to 10000m3Flow rate of/h passes through the main body equipment, and treated flue gas SO2The emission concentration of NO and NO are both less than 35mg/m3。
2. The normal D201SC anion exchange resin is adopted, the smoke passes through the ion exchange resin, and the regeneration needs to be stopped under the condition of no oxidant spray.
Comparative example 2
Using D201SC anion exchange resin, introducing a gas oxidant, referring to CN111359409A (anion exchange resin desulfurization and denitrification method):
1. flue gas pretreatment: flue gas containing SO2The concentration is 500-2000 mg/m3The concentration of NO is 200-800 mg/m3Starting the induced draft fan, cooling the flue gas by the flue gas heat exchanger to 10000m3Flow rate of/h passes through the main body equipment, and treated flue gas SO2The emission concentration of NO and NO are both less than 35mg/m3。
2. Pressurizing by a booster pump, injecting the treated industrial flue gas into a gas mixing chamber, introducing ozone for reaction, controlling the molar ratio of the ozone to the nitric oxide to be 1.5, enabling a gas oxidant to pass through ion exchange resin, and omitting a step of recovering a spraying solution.
Comparative example 3
1. Flue gas pretreatment: flue gas containing SO2The concentration is 500-2000 mg/m3The concentration of NO is 200-800 mg/m3Starting the induced draft fan, cooling the flue gas by the flue gas heat exchanger to 10000m3Flow rate of/h passes through the main body equipment, and treated flue gas SO2The emission concentration of NO and NO are both less than 35mg/m3。
2. Spraying an oxidant solution: the spray oxidizer solution had a composition of 2.5% NaClO + 1% NaOH.
Preparing an oxidant solution with a diameter of about 3.5m in advance in a liquid spraying pool3(ii) a In the operation process of the main equipment, the pump 1 and the valve 1 are started to control the flow of the drenching liquid to be 16m3Perh (flow rate about 2 times resin volume, liquid pouring time about 6 minutes, and liquid pouring amount of 1.6m in total3Equivalent to 0.2 times of the volume of the resin) and then the pump 1 and the valve 1 are closed.
The regeneration process adopts integral shutdown regeneration, which is different from the intermittent spray regeneration of the example 1.
TABLE 1 desulfurization and denitrification process efficiency of examples and comparative examples
Figure BDA0003159424810000131
Figure BDA0003159424810000141
Comparing the resin regeneration process of example 1 with that of comparative example 1, it can be seen that the ion exchange resin of example 1 of the present application can realize the functions of desulfurization, denitrification, oxidation, exchange and partial regeneration by spraying an oxidant solution, does not need to be shut down and stop production, and has a small amount of oxidant (i.e. partial regenerant); comparative example 1 requires shutdown for the entire regeneration of the resin, which not only consumes the construction period, but also requires spare equipment, and has large floor space, expensive investment cost and high operation cost.
By examining the using amounts of the regenerants in the example 1 and the comparative example 3, as can be seen from table 2, the comparative example 3 adopts shutdown resin for overall regeneration, the using amount of the regenerant is large, and the consumption amount of the regenerant in unit time is too much under the condition of the same flue gas treatment amount; while the embodiment 1 adopts a mode of intermittently spraying the regenerant without shutdown, and under the condition of realizing the same flue gas treatment capacity and reaching the standard time, the embodiment 1 adopts the resin volume with the usage amount of the oxidant (namely, part of the regenerant) being only 0.2 times, so that the consumption amount of the regenerant in unit time is less, the cost can be saved by partially regenerating the resin, and the operation cost can be reduced.
As can be seen from the example 1 and the comparative example 2, compared with a gas oxidant, the liquid oxidant is preferably selected, and the liquid oxidant with a proper concentration is prepared in a spraying manner, so that the oxidation and ion exchange efficiencies can be improved, the spraying operation is simple, the cost is low, and the operation conditions are simple and easy to control; and the intermittent spraying can realize the partial regeneration of the resin, thereby saving the process of regenerating the resin, simplifying the process and reducing the production cost.
Table 2 use of regenerants in example 1 and comparative example 3
Figure BDA0003159424810000151
R-resin volume in Table 2
The method adopts the process of liquid oxidant + ion exchange, utilizes the basic principle of ion exchange, changes the form of an exchange group of the ion exchange resin, enables the ion exchange resin to become an oxidant with the effect of a strong oxidant, and the ion exchange resin has the ion exchange function, thereby achieving the purpose of simultaneous desulfurization and denitrification (the desulfurization efficiency reaches 99.5 percent, and the denitrification efficiency is more than 98 percent). Moreover, the oxidant also has the effect of a regenerant, can partially regenerate the resin in an intermittent spraying mode, simultaneously realize transformation, simultaneously meet the integrated process of desulfurization, denitrification, oxidation, exchange and regeneration of the exchange resin, break through the routine of shutdown regeneration of the resin, reduce the using amount of the regenerant and save one-time investment.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present application, "plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
It will be understood by those skilled in the art that the foregoing embodiments are provided merely for clarity of disclosure and are not intended to limit the scope of the invention. Other variations or modifications will occur to those skilled in the art based on the foregoing disclosure and are still within the scope of the present application.

Claims (10)

1. A method for intermittently spraying ion exchange resin material for partial regeneration is characterized in that oxidant solution is intermittently sprayed and passes through an ion exchange resin layer at a certain flow rate, and ion exchange resin is partially regenerated;
the interval of the intermittent spraying is 4-72 hours, and the spraying time is 4-8 min-Secondly, the liquid spraying amount of the oxidant spraying solution is 1/4-1/8 resin volume dosage each time; the oxidant is K2Cr2O7、NaClO、Ca(ClO)2、NaClO2、H2O2、KMnO4One or more of (a).
2. A method for treating exhaust gas using ion exchange resin, comprising the steps of:
flue gas pretreatment: the treatment comprises the processes of dust removal and temperature reduction of the flue gas;
resin oxidation: intermittently spraying an oxidant solution, wherein the oxidant solution passes through the resin layer at a certain flow rate to enable the ion exchange resin to become an oxidized ion exchange resin;
and (3) desulfurization and denitrification: SO in flue gas2,NOxOxidation product H of (2)2SO4、HNO3And H2SO3Meanwhile, the catalyst is adsorbed by ion exchange resin, so that the desulfurization and the denitrification are realized simultaneously;
and (3) recycling the solution: and (4) recycling the oxidant spraying solution, and recycling the regenerated waste liquid.
3. The method according to claim 2, characterized in that the flue gas pre-treatment step is a flue gas temperature reduction to 40-90 ℃, preferably to 50-70 ℃ using a flue gas-water heat exchanger or a flue gas cooling system.
4. The method of claim 2, wherein the resin oxidation step comprises: oxidation reaction and hydration reaction of the flue gas; the oxidation reaction comprises a liquid oxidation reaction and a solid oxidation reaction process.
5. The method of claim 2, wherein the ion exchange resin is a macroporous strongly or weakly basic anion exchange resin and the anion exchange resin comprises one of quaternary amine functional groups, secondary amine functional groups, primary amine functional groups, or tertiary amine functional groups.
6. The method of claim 2, wherein the oxidant is K2Cr2O7、NaClO、Ca(ClO)2、NaClO2、H2O2、KMnO4One or more of (a).
7. The method of claim 5 wherein the oxidizer spray solution comprises a quantity of a base solution selected from the group consisting of NaOH, KOH and NaHCO3,Na2CO3One or more of ammonia; the oxidant spraying solution contains oxidant 0.3-4 wt%, alkali solution 1-6 wt% and water for the rest, based on 100%.
8. The method according to claim 6, wherein the intermittent spraying specifically means that the oxidant solution is sprayed for a time interval of 4 to 72 hours, preferably 4 to 36 hours; spraying for 4-8 min/time; the liquid spraying amount is 1/4-1/8 resin volume dosage/time, and the resin is partially regenerated in the intermittent spraying process.
9. The method of claim 2, wherein the flue gas SO is desulfurized and denitrated2The concentration is less than or equal to 35mg/m3，NOxThe concentration is less than or equal to 50mg/m, the flow speed of the smoke is 1000-3000m3/h/m3The space flow rate of the resin R.
10. The method as claimed in claim 2, wherein sulfate, sulfite and nitrate in the regeneration waste liquid are treated by a strong basic anion exchange column ROH, and the alkaline solution is completely recovered and used for preparing the oxidant spraying solution again; optionally, after the ROH type ion exchange column is saturated, NaOH solution with a certain concentration and with a volume twice that of the resin is used for regeneration, the former time of regenerated waste liquid is discharged, and the latter time of regenerated waste liquid is reserved for recycling in next regeneration.
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