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CN110124490B - Method and device for treating multi-pollutant flue gas and recycling wastewater by using activated carbon - Google Patents

Method and device for treating multi-pollutant flue gas and recycling wastewater by using activated carbon Download PDF

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CN110124490B
CN110124490B CN201810105832.8A CN201810105832A CN110124490B CN 110124490 B CN110124490 B CN 110124490B CN 201810105832 A CN201810105832 A CN 201810105832A CN 110124490 B CN110124490 B CN 110124490B
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flue gas
activated carbon
sulfur
gas
ammonia
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CN110124490A (en
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叶恒棣
杨本涛
魏进超
刘昌齐
黄伏根
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Zhongye Changtian International Engineering Co Ltd
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Zhongye Changtian International Engineering 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
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/38—Removing components of undefined structure
    • B01D53/44—Organic components
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/64—Heavy metals or compounds thereof, e.g. mercury
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76—Gas phase processes, e.g. by using aerosols
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact

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Abstract

A method for treating multi-pollutant flue gas and recycling wastewater by using activated carbon comprises the following steps: 1) adsorption of the polluted flue gas: treating the multi-pollutant smoke by using activated carbon to obtain adsorption saturated activated carbon; 2) thermal regeneration of activated carbon: heating the adsorption saturated activated carbon to high temperature for thermal regeneration; 3) SRG gas treatment: carrying out wet washing on SRG gas generated by the thermal regeneration of the activated carbon to obtain high-sulfur gas and acidic washing wastewater; 4) high-sulfur gas treatment: recycling sulfur resources from the high-sulfur gas obtained in the step 3) through a sulfur resource recycling process; 5) acid washing wastewater treatment: filtering the acidic washing wastewater obtained in the step 3) through acidity to obtain clear liquid and carbon powder; 6) and (3) clear liquid post-treatment: and (3) carrying out an oxidation process on the clear liquid obtained in the step 5), and then carrying out a flocculation precipitation process to obtain metal-containing sludge and salt-containing wastewater. The method of the invention can well treat secondary pollutants, change waste into valuable, recycle, save cost, recycle resources and protect environment.

Description

Method and device for treating multi-pollutant flue gas and recycling wastewater by using activated carbon
Technical Field
The invention relates to a method for treating multi-pollutant flue gas, in particular to a method and a device for treating multi-pollutant flue gas by using activated carbon and recycling waste water. Belonging to the field of resource environment protection.
Background
In the conventional industries of steel, electricity, color, petrifaction, chemical industry or building materials and the like, the raw material seeds are usedMany kinds, often producing various pollutants, such as SO2NOx, dust, VOCs, heavy metals, etc. As the national environmental regulations and standards become stricter, strict limits on the emission of various secondary pollutants, in addition to the primary pollutants, have been gradually proposed. For example, the emission standards of NOx, dioxin pollutants and fluoride are increased by the emission standard of atmospheric pollutants for the steel sintering and pellet industry (GB28662-2012) issued by the national environmental protection ministry in 2012. This makes the flue gas treatment technology to dust and SO2The treatment of single pollutant is changed into the comprehensive treatment of various pollutants, and new requirements are provided for the treatment technology of the smoke pollution of the multiple pollutants.
At present, the multi-pollutant flue gas treatment method is mainly based on a combined mode, such as SCR denitration and desulfurization. However, the method has the problems that the multi-pollutant cooperative treatment is difficult, and the increase of the multi-pollutant can sharply increase the treatment flow, so that the occupied area of an environment-friendly unit is large, the operation cost is high and the like. The currently commonly adopted methods are: the activated carbon is used for treating the multi-pollutant flue gas, and then the activated carbon used for treating the multi-pollutant flue gas is analyzed and recycled, so that the method can well treat the multi-pollutant flue gas to reach the emission standard; however, the activated carbon which has treated the smoke with multiple pollutants generates secondary pollutants such as solid, waste water and the like in the desorption process, which is a difficult problem which always troubles the field.
In the face of the urgent requirements of the acute contradiction between industrial development and air pollution and the overall improvement of the ecological environment quality, the research and development of a multi-pollutant cooperative treatment technology which has high pollutant removal efficiency, low investment and safe operation is urgently needed, and the resource utilization of byproducts is realized. The flue gas pollution emission control technology of the activated carbon utilizes the characteristics of rich functional groups and larger specific surface area of the activated carbon and can simultaneously remove SO2And pollutants such as NOx, dust, VOCs, heavy metals and the like, and the activated carbon with saturated adsorption can be recycled after regeneration, so that the method has a wide development prospect. The active carbon smoke control technology has been developed for more than fifty years so far, and a series of processes are developed at home and abroad successively, and representative processes comprise a Reinluft process, a Sumitomo process and a Westvaco process.
Although the activated carbon smoke control technology can realize the synergistic removal of multiple pollutants, in practice, the pollutants are only enriched through adsorption-desorption, and the problem of secondary pollution exists. If the carbon powder generated in the adsorption and desorption process is not effectively utilized, the desorption gas washing wastewater cannot be effectively treated, and the tail gas after the sulfur resource recovery of the high-concentration sulfur dioxide flue gas generated after desorption does not reach the standard, the popularization and the application of the active carbon flue gas control technology are seriously limited. Because the industrial use time of the activated carbon smoke control technology in China is short, the problems are newer and the treatment difficulty is higher, no identifiable process technology exists internationally, and complete independent innovation is needed urgently.
Disclosure of Invention
The invention provides a treatment method based on a large amount of research and engineering practice, and provides a method for treating multi-pollutant flue gas by using activated carbon and recycling wastewater. The method can well treat secondary pollutants, change waste into valuable, recycle the waste, save cost, recover resources and protect the environment.
By adopting the method, the activated carbon is thermally regenerated after the multi-pollutant flue gas is treated by the activated carbon, so that the activated carbon is recycled. SRG gas generated in the process of thermal regeneration is washed by a wet method, and sulfur resources are recovered; the waste water generated by wet washing is changed into clean water through the processes of filtering, oxidizing, flocculating settling, removing ammonia, crystallizing and the like, and the clean water is circulated to the wet washing procedure for repeated use. The method can realize the dual-circulation cleaning treatment of the multi-pollutant flue gas by the activated carbon and the process water.
According to the first embodiment provided by the invention, the method for treating multi-pollutant flue gas and recycling wastewater by using the activated carbon is provided.
A method for treating multi-pollutant flue gas and recycling wastewater by using activated carbon comprises the following steps:
1) adsorption of the polluted flue gas: conveying multi-pollutant flue gas to a flue gas adsorption device through a flue gas conveying pipeline, wherein activated carbon is filled in the flue gas adsorption device, and the multi-pollutant flue gas is treated by the activated carbon to obtain adsorption saturated activated carbon;
2) thermal regeneration of activated carbon: conveying the adsorption saturated activated carbon to an activated carbon thermal regeneration device, heating the adsorption saturated activated carbon to a high temperature, and performing thermal regeneration;
3) and (3) processing of SRG gas: carrying out wet washing on SRG gas generated by the thermal regeneration of the activated carbon by using a wet washing device to obtain high-sulfur gas and acidic washing wastewater;
4) and (3) treating high-sulfur gas: recycling sulfur resources from the high-sulfur gas obtained in the step 3) through a sulfur resource recycling process;
5) treatment of acidic washing wastewater: filtering the acidic washing wastewater obtained in the step 3) through acidity to obtain clear liquid and carbon powder;
6) and (3) post-treatment of clear liquid: and (3) carrying out an oxidation process on the clear liquid obtained in the step 5), and then carrying out a flocculation precipitation process to obtain metal-containing sludge and salt-containing wastewater.
Preferably, the method further comprises: 7) the high-alkali ammonia removal process comprises the following steps: adding strong base into the salt-containing wastewater obtained in the step 6) to obtain an ammonia-containing byproduct and ammonia-removing wastewater.
Preferably, the method further comprises: 8) condensation and crystallization: cooling and condensing the ammonia-removal wastewater obtained in the step 7) to obtain crystalline salt and clean water. Preferably, the clean water is recycled to the wet scrubbing unit.
Preferably, the method further comprises: 9) metal recovery: and (3) carrying out a metal recovery process on the metal-containing sludge obtained in the step 6) to recover metals.
In the invention, the high-alkali ammonia removal process specifically comprises the following steps: adding strong base into the salt-containing wastewater obtained in the step 6); adjusting the pH value of the salt-containing wastewater to 10-14, preferably 10.5-13.5, more preferably 11-13; separating and recovering ammonia to obtain ammonia-containing by-product and ammonia-removing waste water.
Preferably, the separation adopts one or more of blowing ammonia removal, membrane separation and ammonia removal by evaporation.
In the invention, the condensation crystallization is specifically as follows: adjusting the temperature of the ammonia removal wastewater obtained in the step 7) to low temperature, and condensing and crystallizing salt in the ammonia removal wastewater to obtain crystallized salt and clean water.
Preferably, the low temperature is 0 to 30 ℃, preferably 5 to 25 ℃, more preferably 10 to 20 ℃.
Preferably, the crystalline salt is one or more of sulfate, chloride and fluoride.
In the present invention, the oxidation in step 6) is one or more of chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation or medicament oxidation.
In the invention, the flocculation precipitation process in the step 6) specifically comprises the following steps: adding mixed alkali into the clear liquid obtained in the step 5), adjusting the pH of the clear liquid to be alkalescent, and performing flocculating settling through weak alkali to obtain metal-containing sludge and salt-containing wastewater.
Preferably, the pH of the serum is adjusted to 7-10, preferably 7.2-9, more preferably 7.5-8.5.
In the invention, the mixed alkali is OH-containing-And CO3 2-A mixture of constituents, or containing OH-And HCO3 -A mixture of components. Preferably, the mixed base is a mixture of a lyotropic hydroxide and a lyotropic carbonate, or a mixture of a lyotropic hydroxide and a lyotropic bicarbonate. More preferably, the mixed alkali is a mixture of one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide and one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Preferably, in the step 2), the activated carbon after thermal regeneration is sieved to obtain large-particle activated carbon and small-particle activated carbon. And returning the large-particle activated carbon to the flue gas adsorption device in the step 1) for recycling. The small-particle activated carbon is synthesized into large-particle activated carbon through a carbon powder recycling process, and the large-particle activated carbon is returned to the flue gas adsorption device in the step 1) for recycling or used as fuel.
Preferably, the carbon powder obtained in the step 5) is used for synthesizing large-particle activated carbon and is returned to the flue gas adsorption device in the step 1) for recycling or used as fuel through a carbon powder recycling process.
Preferably, the carbon powder recycling step is performed by regrinding, burning or landfill.
In the invention, sulfur-containing byproducts and sulfur-containing tail gas are obtained in the sulfur recycling process in the step 4).
Preferably, the sulfur-containing tail gas is conveyed to a flue gas conveying pipeline and recycled to the step 1).
Preferably, the strong base in step 7) is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the invention, the multi-pollutant flue gas is SO2And one or more of NOx, dust, VOCs and heavy metals.
In the invention, the multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in the steel, electric, colored, petrochemical, chemical or building material industries.
Preferably, the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%, preferably 0.03-0.8%, and more preferably 0.05-0.5%.
In the invention, the temperature of the multi-pollutant flue gas is 100-200 ℃, preferably 120-180 ℃, and more preferably 130-160 ℃.
In the invention, the multi-pollutant flue gas in the step 1) is treated by using activated carbon, specifically, the activated carbon is used for adsorbing the multi-pollutant flue gas, and the activated carbon is used for adsorbing pollutants in the multi-pollutant flue gas.
Preferably, the adsorption is cross-flow adsorption or countercurrent adsorption.
In the invention, in the step 1), when the multi-pollutant flue gas contains NOx, ammonia gas is sprayed into the flue gas adsorption device.
Preferably, the molar amount of the ammonia gas injected in a unit time is 0.8 to 2 times, preferably 0.9 to 1.5 times, and more preferably 1.0 to 1.3 times the molar amount of the NOx contained in the flue gas flow in the unit time.
In the invention, the thermal regeneration is to heat the activated carbon with saturated adsorption by adopting electric heating or hot air heating.
Preferably, the temperature of the thermal regeneration is from 250 ℃ to 480 ℃, preferably from 300 ℃ to 450 ℃, more preferably from 360 ℃ to 430 ℃.
In the present invention, the wet scrubbing is carried out using an acidic solution (e.g., a 0.5-10% strength dilute hydrochloric acid or dilute sulfuric acid or dilute phosphoric acid solution; the strength is, for example, 1 wt%, 4 wt%, 5 wt%, or 7 wt%).
Preferably, the pH value of the acidic solution is 0 to 7, preferably 1 to 6, and more preferably 2 to 5.
In the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 10-100, preferably 1: 20-80, and more preferably 1: 30-60.
In the present invention, the sulfur-recycling step specifically includes: converting high-sulfur gas into sulfur-containing by-products, wherein the sulfur-containing by-products are sulfuric acid, sulfur and liquid SO2Sulfite, sulfate, more preferably high sulfur gas to sulfuric acid.
In the invention, the acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants. Preferably, the metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
In the invention, the acidic filtration is to remove suspended matters by utilizing the self gravity settling action or the interception action of a filter. The concentration of suspended matters in the clear liquid after acidic filtration is 0-100 mg/L, preferably 1-80 mg/L, and more preferably 2-50 mg/L.
Preferably, the crystalline salt obtained in step 8) is further dried by hot air and then subjected to a dust removal treatment.
Preferably, the dust removal treatment adopts dry dust removal, preferably one of electric dust removal, cloth bag dust removal and ceramic dust removal, and more preferably cloth bag dust removal.
According to a second embodiment provided by the invention, a device for the synergistic treatment of multi-pollutant flue gas and zero discharge of wastewater is provided.
The device comprises a flue gas conveying pipeline, a flue gas adsorption device, an active carbon thermal regeneration device, a wet washing device, a sulfur recycling device, an acid filtering device, an oxidation device and a flocculation precipitation device. The multi-pollutant flue gas is conveyed to the flue gas adsorption device through a flue gas conveying pipeline. The active carbon outlet of the flue gas adsorption device is connected to the active carbon thermal regeneration device through a conveying device. And an SRG gas outlet of the activated carbon thermal regeneration device is connected to the wet scrubbing device through a pipeline. And a high-sulfur gas outlet of the wet scrubbing device is connected to a sulfur recycling device. The waste water outlet of the wet scrubbing device is connected to the acidic filtering device. The liquid outlet of the acid filtration device is connected to the oxidation device. The outlet of the oxidation device is connected to the flocculation precipitation device.
Preferably, the device also comprises a high-alkali ammonia removal device and a condensation crystallization device. The liquid outlet of the flocculation precipitation device is connected to a high-alkali ammonia removal device. And a liquid outlet of the high-alkali ammonia removal device is connected to the condensation crystallization device. And a clean water outlet of the condensation crystallization device is connected to the wet washing device.
Preferably, the device also comprises a screening device and a carbon powder recycling device. And an activated carbon outlet of the activated carbon thermal regeneration device is connected to the screening device. And a large-particle activated carbon outlet of the screening device is connected to the flue gas adsorption device. The small particle activated carbon outlet of the screening device and the solid outlet of the acidic filtering device are connected to the carbon powder recycling device. The discharge port of the carbon powder recycling device is connected to the flue gas adsorption device.
Preferably, the apparatus further comprises a metal recovery device. The solid outlet of the flocculation precipitation device is connected to a metal recovery device.
Preferably, a sulfur-containing tail gas outlet of the sulfur recycling device is connected to a flue gas conveying pipeline or a flue gas adsorption device.
Preferably, the flue gas adsorption unit is an adsorption tower, and the activated carbon thermal regeneration unit is a desorption tower.
The invention provides a method for cleaning and treating multi-pollutant flue gas by active carbon and process water double circulation, which has the following technical process and technical principle:
a)SO2resource utilization and deep purification:based on the characteristics of rich functional groups and large specific surface area on the surface of the activated carbon, the low-concentration SO in the flue gas2The activated carbon is selectively adsorbed to realize the purification of the flue gas, and the saturated activated carbon is reasonably thermally desorbed to obtain high-concentration SO with higher purity2. High concentration of SO2Respectively oxidizing, reducing, concentrating, and absorbing with sulfuric acid, sulfur, and liquid SO2And recovering the sulfate. The tail gas which is not effectively recycled returns to the active carbon gas inlet for cyclic removal, SO that SO is realized2Resource utilization and deep purification.
b) And (3) NOx is harmless: because the active carbon has strong reducibility, nitrogen oxides in the flue gas can be converted into nitrogen gas through non-SCR reaction on the surface of the active carbon. In addition, the activated carbon has abundant surface functional groups, and can perform SCR reaction through surface catalysis in the presence of ammonia gas to convert nitrogen oxides into nitrogen. The two approaches can convert the nitrogen oxide into harmless nitrogen, and realize the harmless treatment of the NOx.
c) Harmless treatment of dioxin: the dioxin is firstly adsorbed in the activated carbon to realize flue gas purification, and then is cracked and converted into harmless substances through the catalytic action of the activated carbon in the thermal desorption process of the activated carbon, and the experimental result shows that the dioxin can be thoroughly decomposed by keeping the temperature of 400 ℃ in the desorption tower for more than 1.5 h.
d) Reduction of solid waste containing heavy metals: after the heavy metal is adsorbed by the active carbon, most of the heavy metal can enter desorption gas through desorption and then is washed and purified to enter washing wastewater. The method reasonably analyzes the characteristics of each pollutant and combines the step-by-step treatment with mixed alkali (OH)-And CO3 2-) The weak base flocculates and precipitates heavy metals, so that the heavy metal sludge amount is greatly reduced, namely the dangerous solid waste amount is reduced.
e) Ammonia nitrogen clean recovery: after ammonia enters flue gas, part of ammonia and SO2The binding becomes ammonium sulfite and a portion reacts with NOx in an SCR reaction to form nitrogen. Because the ammonium sulfite is unstable, the generated ammonium sulfite is easily decomposed into ammonia gas and SO in the high-temperature regeneration process of the active carbon2. Since ammonia is very soluble in water, almost all ammonia enters the washing wastewater. Hair brushThe technology of precipitating heavy metals in weak alkali (7-9) and removing ammonia or recovering ammonia in high alkali (11-14) is adopted, so that ammonia gas escaping caused by heavy metal precipitation in high alkali can be effectively avoided, a metal ammonia nitrogen stable complex is formed, and clean recovery or treatment of ammonia nitrogen is realized.
f) Harmlessness of fluorine and chlorine: fluorine and chlorine in the flue gas are easily adsorbed by the activated carbon, and then desorbed at high temperature and enter the washing wastewater. Because the solubility of the fluorine chloride salt in water is reduced along with the reduction of the temperature, the method adopts the reduction of the solution temperature to separate out the fluorine chloride salt crystals after the heavy metal and ammonia nitrogen in the wastewater are removed. The problems of co-precipitation with heavy metals and difficult crystallization of ammonium salt are avoided, the harmfulness of the crystallized salt is reduced, and harmless treatment of fluorine and chlorine is realized.
g) Carbon powder recycling: a large amount of activated carbon powder is generated in the processes of activated carbon adsorption and desorption due to chemical loss and mechanical loss, a part of the carbon powder is separated after being screened with the desorbed activated carbon, and a part of the carbon powder enters the wastewater with the desorbed gas. Based on the particle size analysis and the surface hydrophobic characteristic of the carbon powder, the method filters the carbon powder in the wastewater under the acidic condition by reasonably designing the filtering condition, and mixes the carbon powder with the carbon powder under the sieve after drying, so that the carbon powder is granulated, combusted and buried, the resource utilization of the carbon powder is realized, and the operation cost is reduced.
In the invention, after the activated carbon adsorbing the pollutants passes through an activated carbon thermal regeneration device (such as an desorption tower), the pollutants originally adsorbed on the activated carbon enter desorption gas, and the activated carbon with saturated adsorption is changed into fresh activated carbon (namely the activated carbon capable of being used for adsorbing the pollutants by an adsorption tower). The activated carbon discharged from the desorption tower generates a large amount of activated carbon powder due to mechanical loss, the activated carbon is screened by a screening device, large-particle activated carbon is returned to the flue gas adsorption device in the step 1) for recycling, and small-particle activated carbon is synthesized into large-particle activated carbon through a carbon powder recycling process and is returned to the flue gas adsorption device in the step 1) for recycling or used as fuel; so that the activated carbon is recovered and recycled.
In the present invention, the desorption gas, i.e. SRG gas, is washed by wet method, so that a part of carbon powder attached in the SRG gas enters the wastewater along with the desorption gas, and metal ions are dissolved in the water. The sulfur-containing gas is still gaseous, the high-sulfur gas is collected, sulfur resources are recovered through a sulfur resource recycling process, and the remaining extremely small part of sulfur-containing tail gas is conveyed to a flue gas conveying pipeline and then treated by an adsorption tower. Realizing zero emission of the polluted gas.
In the invention, after wet washing, the generated acidic washing wastewater comprises carbon powder and metal ions in a suspended state; the part of the acidic washing wastewater is subjected to acidic filtration to separate suspended matters (namely carbon powder) in the wastewater to obtain carbon powder, and the part of the carbon powder can be recycled through a carbon powder recycling process, for example, a re-granulation process is adopted to obtain large-particle activated carbon, and then the large-particle activated carbon is recycled to an adsorption tower. The wastewater after the suspended matter is separated contains metal ions (or metal salts) which are clear liquid; removing COD in the clear liquid after the acid washing through an oxidation process, so that organic matter components in the clear liquid are greatly reduced; heavy metal ions are removed from the sludge through flocculation precipitation, and the metal ions enter the metal-containing sludge, and then are collected and enriched through a metal recovery process, and are sold or used for other purposes. Removing ammonia in the salt-containing wastewater after the flocculation precipitation procedure through a high-alkali ammonia removal process to obtain an ammonia-containing byproduct and ammonia-removed wastewater; the ammonia-containing by-product can be directly sold, and economic value is generated. Removing chloride ions and fluoride ions from the ammonia-removing wastewater through condensation and crystallization; obtaining crystal salt and clean water; the crystal salt is sulfate, chloride or fluoride. The crystallized salt can be sold directly, resulting in economic value. The rest of crystallization process water is recycled to the wet washing procedure and can be recycled.
By adopting the method, after the multi-pollutant smoke is treated by the activated carbon, the activated carbon can be completely recycled. The sulfides in the contaminants are recovered as sulfur-containing by-products. Most of the metal ions can be recovered through a flocculation precipitation process and a metal recovery process, the rest is changed into crystal salt, nitrogen oxide is changed into nitrogen in the analysis process, and organic matters are changed into carbon dioxide through an oxidation process. Therefore, the synergistic treatment of the multi-pollutant flue gas is really realized, the zero discharge of waste water is realized, the secondary pollution is not generated, and metal ions (or heavy metal ions) in the multi-pollutant flue gas are recovered. Changing waste into valuable, recycling and realizing zero discharge of wastewater; saving cost, recovering resources and protecting environment.
In the invention, the SRG gas refers to the enriched flue gas discharged after being analyzed by the desorption tower. The SRG gas (or SRG flue gas) has high temperature, high dust content and SO2High content, high water content, complex smoke impurity components and the like. In the art, SRG gas is also referred to simply as sulfur-rich gas; used for being conveyed to an acid making system for making acid.
Compared with the prior art, the method has the following beneficial technical effects:
(1) the invention carries out reasonable design aiming at the respective characteristics of multiple pollutants in the flue gas, and realizes the deep purification, resource or harmless treatment/disposal of each pollutant.
(2) The invention realizes the double-cycle recycling of the activated carbon and the industrial water by the carbon powder recycling and the reasonable step-by-step treatment of the washing wastewater, and greatly reduces the energy consumption and the material consumption.
(3) When the sulfur recycling process fails to effectively treat high-concentration sulfur dioxide, low-concentration sulfur dioxide tail gas can be generated, and the tail gas can be returned to the flue gas for absorption because the low-concentration sulfur dioxide is taken as a treatment object in the invention, and no tail gas treatment facility is required to be additionally arranged, so that the investment cost is greatly reduced.
(4) The method reasonably classifies and separates the heavy metals and the crystallized salt material flow with less harm, and avoids the defects of large sludge amount and complex components caused by the conventional limestone method.
(5) The invention adopts the process of flocculating settling of mixed alkali and weak alkali coupled with high alkali ammonia removal, thereby avoiding ammonia gas escape and forming a metal ammonia nitrogen stable complex caused by heavy metal precipitation of high alkali and realizing clean recovery or treatment of ammonia nitrogen.
In conclusion, the method for cleaning and treating multi-pollutant flue gas by using activated carbon and process water dual-circulation, provided by the invention, has the advantages of multi-pollutant cooperative treatment, low operation cost, equipment investment saving, cleaning and treatment and effective control of secondary pollution.
Drawings
FIG. 1 is a process flow diagram of a method for treating multi-pollutant flue gas and recycling wastewater by using activated carbon according to the invention;
FIG. 2 is another process flow diagram of a method for treating multi-pollutant flue gas and recycling wastewater by using activated carbon according to the present invention;
FIG. 3 is a schematic structural diagram of an apparatus for treating multi-pollutant flue gas and recycling wastewater by using activated carbon according to the present invention.
Reference numerals: l1: a flue gas conveying pipeline; 1: a flue gas adsorption device; 2: an activated carbon thermal regeneration device; 3: a wet scrubbing apparatus; 4: a sulfur recycling device; 5: an acidic filtration unit; 6: an oxidation unit; 7: a flocculation precipitation device; 8: a high-alkali ammonia removal device; 9: a condensation crystallization device; 10: a screening device; 11: a carbon powder recycling device; 12: a metal recovery device.
Detailed Description
According to the first embodiment provided by the invention, the method for treating multi-pollutant flue gas and recycling wastewater by using the activated carbon is provided.
A method for treating multi-pollutant flue gas and recycling wastewater by using activated carbon comprises the following steps:
1) adsorption of the polluted flue gas: conveying multi-pollutant flue gas to a flue gas adsorption device 1 through a flue gas conveying pipeline L1, wherein activated carbon is filled in the flue gas adsorption device 1, and the multi-pollutant flue gas is treated by the activated carbon to obtain adsorption saturated activated carbon;
2) thermal regeneration of activated carbon: conveying the adsorption saturated activated carbon to an activated carbon thermal regeneration device 2, heating the adsorption saturated activated carbon to a high temperature, and performing thermal regeneration;
3) and (3) processing of SRG gas: carrying out wet washing on SRG gas generated by the thermal regeneration of the activated carbon by using a wet washing device 3 to obtain high-sulfur gas and acidic washing wastewater;
4) and (3) treating high-sulfur gas: recycling sulfur resources from the high-sulfur gas obtained in the step 3) through a sulfur resource recycling process;
5) treatment of acidic washing wastewater: filtering the acidic washing wastewater obtained in the step 3) through acidity to obtain clear liquid and carbon powder;
6) and (3) post-treatment of clear liquid: and (3) carrying out an oxidation process on the clear liquid obtained in the step 5), and then carrying out a flocculation precipitation process to obtain metal-containing sludge and salt-containing wastewater.
Preferably, the method further comprises: 7) the high-alkali ammonia removal process comprises the following steps: adding strong base into the salt-containing wastewater obtained in the step 6) to obtain an ammonia-containing byproduct and ammonia-removing wastewater.
Preferably, the method further comprises: 8) condensation and crystallization: cooling and condensing the ammonia-removal wastewater obtained in the step 7) to obtain crystalline salt and clean water. Preferably, the clean water is recycled to the wet scrubbing apparatus 3.
Preferably, the method further comprises: 9) metal recovery: and (3) carrying out a metal recovery process on the metal-containing sludge obtained in the step 6) to recover metals.
In the invention, the high-alkali ammonia removal process specifically comprises the following steps: adding strong base into the salt-containing wastewater obtained in the step 6); adjusting the pH value of the salt-containing wastewater to 10-14, preferably 10.5-13.5, more preferably 11-13; separating and recovering ammonia to obtain ammonia-containing by-product and ammonia-removing waste water.
Preferably, the separation adopts one or more of blowing ammonia removal, membrane separation and ammonia removal by evaporation.
In the invention, the condensation crystallization is specifically as follows: adjusting the temperature of the ammonia removal wastewater obtained in the step 7) to low temperature, and condensing and crystallizing salt in the ammonia removal wastewater to obtain crystallized salt and clean water.
Preferably, the low temperature is 0 to 30 ℃, preferably 5 to 25 ℃, more preferably 10 to 20 ℃.
Preferably, the crystalline salt is one or more of sulfate, chloride and fluoride.
In the present invention, the oxidation in step 6) is one or more of chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation or medicament oxidation.
In the invention, the flocculation precipitation process in the step 6) specifically comprises the following steps: adding mixed alkali into the clear liquid obtained in the step 5), adjusting the pH of the clear liquid to be alkalescent, and performing flocculating settling through weak alkali to obtain metal-containing sludge and salt-containing wastewater.
Preferably, the pH of the serum is adjusted to 7-10, preferably 7.2-9, more preferably 7.5-8.5.
In the invention, the mixed alkali is OH-containing-And CO3 2-A mixture of constituents, or containing OH-And HCO3 -A mixture of components. Preferably, the mixed base is a mixture of a lyotropic hydroxide and a lyotropic carbonate, or a mixture of a lyotropic hydroxide and a lyotropic bicarbonate. More preferably, the mixed alkali is a mixture of one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide and one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
Preferably, in the step 2), the activated carbon after thermal regeneration is sieved to obtain large-particle activated carbon and small-particle activated carbon. The large-particle activated carbon is returned to the flue gas adsorption device 1 in the step 1) for recycling. The small-particle activated carbon is synthesized into large-particle activated carbon through a carbon powder recycling process, and the large-particle activated carbon is returned to the flue gas adsorption device 1 in the step 1) for recycling or used as fuel.
Preferably, the carbon powder obtained in step 5) is used for synthesizing large-particle activated carbon through a carbon powder recycling process and is returned to the flue gas adsorption device 1 in step 1) for recycling or used as fuel.
Preferably, the carbon powder recycling step is performed by regrinding, burning or landfill.
In the invention, sulfur-containing byproducts and sulfur-containing tail gas are obtained in the sulfur recycling process in the step 4).
Preferably, the sulfur-containing tail gas is conveyed to a flue gas conveying pipeline L1 to be recycled to the step 1).
Preferably, the strong base in step 7) is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
In the invention, the multi-pollutant flue gas is SO2And one or more of NOx, dust, VOCs and heavy metals.
In the invention, the multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in the steel, electric, colored, petrochemical, chemical or building material industries.
Preferably, the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%, preferably 0.03-0.8%, and more preferably 0.05-0.5%.
In the invention, the temperature of the multi-pollutant flue gas is 100-200 ℃, preferably 120-180 ℃, and more preferably 130-160 ℃.
In the invention, the multi-pollutant flue gas in the step 1) is treated by using activated carbon, specifically, the activated carbon is used for adsorbing the multi-pollutant flue gas, and the activated carbon is used for adsorbing pollutants in the multi-pollutant flue gas.
Preferably, the adsorption is cross-flow adsorption or countercurrent adsorption.
In the invention, in the step 1), when the multi-pollutant flue gas contains NOx, ammonia gas is sprayed into the flue gas adsorption device (1).
Preferably, the molar amount of the ammonia gas injected in a unit time is 0.8 to 2 times, preferably 0.9 to 1.5 times, and more preferably 1.0 to 1.3 times the molar amount of the NOx contained in the flue gas flow in the unit time.
In the invention, the thermal regeneration is to heat the activated carbon with saturated adsorption by adopting electric heating or hot air heating.
Preferably, the temperature of the thermal regeneration is from 250 ℃ to 480 ℃, preferably from 300 ℃ to 450 ℃, more preferably from 360 ℃ to 430 ℃.
In the present invention, the wet scrubbing is carried out using an acidic solution (e.g., a 0.5-10% strength dilute hydrochloric acid or dilute sulfuric acid or dilute phosphoric acid solution; the strength is, for example, 1 wt%, 4 wt%, 5 wt%, or 7 wt%).
Preferably, the pH value of the acidic solution is 0 to 7, preferably 1 to 6, and more preferably 2 to 5.
In the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 10-100, preferably 1: 20-80, and more preferably 1: 30-60.
In the present invention, the sulfur-recycling step specifically includes:converting high-sulfur gas into sulfur-containing by-products, wherein the sulfur-containing by-products are sulfuric acid, sulfur and liquid SO2Sulfite, sulfate, more preferably high sulfur gas to sulfuric acid.
In the invention, the acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants. Preferably, the metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
In the invention, the acidic filtration is to remove suspended matters by utilizing the self gravity settling action or the interception action of a filter. The concentration of suspended matters in the clear liquid after acidic filtration is 0-100 mg/L, preferably 1-80 mg/L, and more preferably 2-50 mg/L.
Preferably, the crystalline salt obtained in step 8) is further dried with hot air and then subjected to a dust removal treatment.
Preferably, the dust removal treatment adopts dry dust removal, preferably one of electric dust removal, cloth bag dust removal and ceramic dust removal, and more preferably cloth bag dust removal.
According to a second embodiment provided by the invention, a device for the synergistic treatment of multi-pollutant flue gas and zero discharge of wastewater is provided.
The device comprises a flue gas conveying pipeline L1, a flue gas adsorption device 1, an activated carbon thermal regeneration device 2, a wet washing device 3, a sulfur recycling device 4, an acid filtering device 5, an oxidation device 6 and a flocculation precipitation device 7. The multi-pollutant flue gas is conveyed to the flue gas adsorption device 1 through a flue gas conveying pipeline L1. The activated carbon outlet of the flue gas adsorption device 1 is connected to the activated carbon thermal regeneration device 2 through a conveying device. The SRG gas outlet of the activated carbon thermal regeneration unit 2 is connected to the wet scrubbing unit 3 by a pipe. The high-sulfur gas outlet of the wet scrubbing device 3 is connected to the sulfur recycling device 4. The waste water outlet of the wet scrubbing unit 3 is connected to an acidic filtration unit 5. The liquid outlet of the acid filter unit 5 is connected to an oxidation unit 6. The outlet of the oxidation device 6 is connected to a flocculation and precipitation device 7.
Preferably, the device also comprises a high-alkali ammonia removal device 8 and a condensation crystallization device 9. The liquid outlet of the flocculation and precipitation device 7 is connected to a high-alkali ammonia removal device 8. The liquid outlet of the high-alkali ammonia removal device 8 is connected to the condensation crystallization device 9. The clean water outlet of the condensation crystallization device 9 is connected to the wet washing device 3.
Preferably, the device further comprises a screening device 10 and a carbon powder recycling device 11. The activated carbon outlet of the activated carbon thermal regeneration device 2 is connected to the screening device 10. The large-particle activated carbon outlet of the screening device 10 is connected to the flue gas adsorption device 1. The small particle activated carbon outlet of the screening device 10 and the solid outlet of the acidic filtering device 5 are connected to a carbon powder recycling device 11. The discharge port of the carbon powder recycling device 11 is connected to the flue gas adsorption device 1.
Preferably, the apparatus further comprises a metal recovery device 12. The solids outlet of the flocculation and precipitation unit 7 is connected to a metal recovery unit 12.
Preferably, the sulfur-containing tail gas outlet of the sulfur recycling device 4 is connected to the flue gas conveying pipeline L1 or the flue gas adsorption device 1.
Preferably, the flue gas adsorption device 1 is an adsorption tower, and the activated carbon thermal regeneration device 2 is an desorption tower.
Example 1
As shown in fig. 3, the device for the synergistic treatment of multi-pollutant flue gas and the zero discharge of wastewater comprises a flue gas conveying pipeline L1, a flue gas adsorption device 1, an activated carbon thermal regeneration device 2, a wet scrubbing device 3, a sulfur recycling device 4, an acidic filtering device 5, an oxidation device 6 and a flocculation precipitation device 7. The multi-pollutant flue gas is conveyed to the flue gas adsorption device 1 through a flue gas conveying pipeline L1. The activated carbon outlet of the flue gas adsorption device 1 is connected to the activated carbon thermal regeneration device 2 through a conveying device. The SRG gas outlet of the activated carbon thermal regeneration unit 2 is connected to the wet scrubbing unit 3 by a pipe. The high-sulfur gas outlet of the wet scrubbing device 3 is connected to the sulfur recycling device 4. The waste water outlet of the wet scrubbing unit 3 is connected to an acidic filtration unit 5. The liquid outlet of the acid filter unit 5 is connected to an oxidation unit 6. The outlet of the oxidation device 6 is connected to a flocculation and precipitation device 7. The flue gas adsorption device 1 is an adsorption tower, and the activated carbon thermal regeneration device 2 is an analytical tower.
Example 2
Example 1 was repeated except that the apparatus further included a high-alkali ammonia removal apparatus 8 and a condensation crystallization apparatus 9. The liquid outlet of the flocculation and precipitation device 7 is connected to a high-alkali ammonia removal device 8. The liquid outlet of the high-alkali ammonia removal device 8 is connected to the condensation crystallization device 9. The clean water outlet of the condensation crystallization device 9 is connected to the wet washing device 3.
The device also comprises a screening device 10 and a carbon powder recycling device 11. The activated carbon outlet of the activated carbon thermal regeneration device 2 is connected to the screening device 10. The large-particle activated carbon outlet of the screening device 10 is connected to the flue gas adsorption device 1. The small particle activated carbon outlet of the screening device 10 and the solid outlet of the acidic filtering device 5 are connected to a carbon powder recycling device 11. The discharge port of the carbon powder recycling device 11 is connected to the flue gas adsorption device 1.
Example 3
Example 2 is repeated except that the apparatus further comprises a metal recovery apparatus 12. The solids outlet of the flocculation and precipitation unit 7 is connected to a metal recovery unit 12. The sulfur-containing tail gas outlet of the sulfur recycling device 4 is connected to the flue gas conveying pipeline L1.
Example 4
As shown in fig. 1, a method for treating multi-pollutant flue gas and recycling wastewater by using activated carbon comprises the following steps:
1) adsorption of the polluted flue gas: conveying multi-pollutant flue gas to a flue gas adsorption device 1 through a flue gas conveying pipeline L1, wherein activated carbon is filled in the flue gas adsorption device 1, and the multi-pollutant flue gas is treated by adopting cross flow adsorption through the activated carbon to obtain adsorption saturated activated carbon;
2) thermal regeneration of activated carbon: conveying the adsorption saturated activated carbon to an activated carbon thermal regeneration device 2, and electrically heating the adsorption saturated activated carbon to 400 ℃ for thermal regeneration;
3) and (3) processing of SRG gas: carrying out wet washing on SRG gas generated by the thermal regeneration of the activated carbon by using a wet washing device 3 to obtain high-sulfur gas and acidic washing wastewater;
4) and (3) treating high-sulfur gas: the high-sulfur gas obtained in the step 3) is subjected to sulfur resource recycling to recover sulfur resources, and the method specifically comprises the following steps: converting the high-sulfur gas into a sulfur-containing byproduct, wherein the sulfur-containing byproduct is sulfuric acid;
5) treatment of acidic washing wastewater: filtering the acidic washing wastewater obtained in the step 3) through acidity, wherein the adopted solution is an acidic solution, and the pH value is 4; the volume flow ratio of the SRG gas to the solution is 1: 50; obtaining clear liquid and carbon powder;
6) and (3) post-treatment of clear liquid: and (3) performing an electrochemical oxidation process on the clear liquid obtained in the step 5), then adding sodium hydroxide and sodium carbonate into the oxidized clear liquid, adjusting the pH of the clear liquid to 8, and performing flocculation and precipitation by using weak base to obtain metal-containing sludge and salt-containing wastewater.
The multi-pollutant flue gas is SO2Dust, VOCs and heavy metals. The volume content of sulfur dioxide in the multi-pollutant flue gas is 0.3 percent; the temperature of the multi-pollutant flue gas is 150 ℃.
In this example, the concentration of the suspension in the supernatant after acidic filtration was 1 mg/L. High-sulfur gas generated in the SRG gas treatment process is completely recycled after the sulfur resource recycling process. Removing COD in the clear liquid after the acid washing through an oxidation process, so that organic matter components in the clear liquid are greatly reduced; then removing heavy metal ions in the salt-containing wastewater through flocculation precipitation, wherein the content of the heavy metal ions in the salt-containing wastewater is 7.2mg/L through a flocculation precipitation process; the salt-containing wastewater reaches the discharge standard and can be directly discharged, and the carbon powder can be recycled.
Example 5
As shown in fig. 2, example 4 is repeated except that the method further comprises:
7) the high-alkali ammonia removal process comprises the following steps: adding sodium hydroxide into the salt-containing wastewater obtained in the step 6); adjusting the pH value of the salt-containing wastewater to 12; separating and recovering ammonia, wherein ammonia is removed by blowing; obtaining ammonia-containing by-products and ammonia-removing wastewater;
8) condensation and crystallization: adjusting the temperature of the ammonia removal wastewater obtained in the step 7) to 15 ℃, and condensing and crystallizing salt in the ammonia removal wastewater to obtain crystallized salt and clean water; the crystal salt is sulfate, chloride or fluoride.
The volume content of sulfur dioxide in the multi-pollutant flue gas is 0.2 percent; the temperature of the multi-pollutant flue gas is 160 ℃.
And (3) recovering sulfuric acid from high-sulfur gas generated in the SRG gas treatment process after a sulfur recycling process, and circulating the residual sulfur-containing tail gas to a flue gas conveying pipeline L1 for centralized treatment. Most heavy metal ions are recovered in the flocculation precipitation process, and ammonia in the salt-containing wastewater after the flocculation precipitation process is removed through a high-alkali ammonia removal process to obtain an ammonia-containing byproduct and ammonia-removed wastewater; the ammonia-containing by-product can be directly sold, and economic value is generated. Removing chloride ions and fluoride ions from the ammonia-removing wastewater through condensation and crystallization; obtaining crystal salt and clean water; the crystal salt is sulfate, chloride or fluoride. The crystallized salt can be sold directly, resulting in economic value.
Example 6
Example 5 was repeated except that the method further included: 9) metal recovery: and (3) carrying out a metal recovery process on the metal-containing sludge obtained in the step 6) to recover metals.
The clean water is recycled to the wet scrubbing unit 3 in step 7).
Step 6) the metal-containing sludge obtained by the weak base flocculation precipitation can be used for recovering valuable metals by the existing metal recovery process; such as iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel, aluminum.
Example 7
Example 6 was repeated except that step 6) was carried out using ultraviolet catalytic oxidation, and then potassium hydroxide and potassium hydrogencarbonate were added to the oxidized clear solution to adjust the pH of the clear solution to 9.
The high-alkali ammonia removal process specifically comprises the following steps: adding strong base into the salt-containing wastewater obtained in the step 6); adjusting the pH value of the salt-containing wastewater to 10; separating and recovering ammonia, wherein membrane separation is adopted for separation; obtaining ammonia-containing by-products and ammonia-removing wastewater. The strong base added in step 7) is potassium hydroxide. In the step 8), the temperature of the ammonia removal wastewater obtained in the step 7) is adjusted to 28 ℃.
Example 8
Example 6 was repeated except that in step 2), the thermally regenerated activated carbon was subjected to sieving to obtain large-grained activated carbon and small-grained activated carbon. The large-particle activated carbon is returned to the flue gas adsorption device 1 in the step 1) for recycling. The small-particle activated carbon is synthesized into large-particle activated carbon through a carbon powder recycling process, and the large-particle activated carbon is returned to the flue gas adsorption device 1 in the step 1) for recycling or used as fuel.
And 4) carrying out a sulfur recycling process to obtain a sulfur-containing byproduct and a sulfur-containing tail gas. The sulfur-containing tail gas is conveyed to a flue gas conveying pipeline L1 and is recycled to the step 1).
The carbon powder obtained in the step 5) is used for synthesizing large-particle activated carbon through a carbon powder recycling process and is returned to the flue gas adsorption device 1 in the step 1) for recycling or used as fuel.
In this embodiment: and screening the activated carbon after thermal regeneration to obtain large-particle activated carbon and small-particle activated carbon. The large-particle activated carbon is returned to the flue gas adsorption device 1 in the step 1) for recycling. The small-particle activated carbon is synthesized into large-particle activated carbon through a carbon powder recycling process and then returned to the flue gas adsorption device 1 in the step 1) for recycling. The carbon powder obtained in the step 5) is used for synthesizing large-particle activated carbon through a carbon powder recycling process and is returned to the flue gas adsorption device 1 in the step 1) for recycling. The embodiment completely realizes the advantages of the synergistic treatment of multi-pollutant flue gas and the effective control of secondary pollution. The method can well treat secondary pollutants, change waste into valuable, recycle, realize zero discharge of wastewater, save cost, recover resources and protect environment.
Example 9
Example 6 was repeated except that the multi-pollutant flue gas was SO2NOx, dust, VOCs and heavy metals. In the step 1), when the multi-pollutant flue gas contains NOx, ammonia gas is sprayed into the flue gas adsorption device (1). Preferably, the molar amount of ammonia injected per unit time is 1 time the molar amount of NOx contained in the flue gas stream per unit time. And (3) treating the multi-pollutant smoke in the step 1) by adopting activated carbon in a countercurrent manner. The heat regeneration in the step 2) is heated to 320 ℃ by hot air.
And 8) further drying the crystalline salt obtained in the step 8) by hot air, and then removing dust.

Claims (55)

1. A method for treating multi-pollutant flue gas and recycling wastewater by using activated carbon comprises the following steps:
1) adsorption of the polluted flue gas: conveying multi-pollutant flue gas to a flue gas adsorption device (1) through a flue gas conveying pipeline (L1), wherein activated carbon is filled in the flue gas adsorption device (1), and the multi-pollutant flue gas is treated by the activated carbon to obtain adsorption saturated activated carbon;
2) thermal regeneration of activated carbon: conveying the adsorption saturated activated carbon to an activated carbon thermal regeneration device (2), heating the adsorption saturated activated carbon to a high temperature, and performing thermal regeneration;
3) and (3) processing of SRG gas: the SRG gas generated by the thermal regeneration of the activated carbon is subjected to wet washing by a wet washing device (3) to obtain high-sulfur gas and acidic washing wastewater;
4) and (3) treating high-sulfur gas: recycling sulfur resources from the high-sulfur gas obtained in the step 3) through a sulfur resource recycling process;
5) treatment of acidic washing wastewater: filtering the acidic washing wastewater obtained in the step 3) through acidity to obtain clear liquid and carbon powder;
6) and (3) post-treatment of clear liquid: subjecting the clear liquid obtained in the step 5) to an oxidation process, and then performing a flocculation precipitation process to obtain metal-containing sludge and salt-containing wastewater;
7) the high-alkali ammonia removal process comprises the following steps: adding strong base into the salt-containing wastewater obtained in the step 6) to obtain an ammonia-containing byproduct and ammonia-removing wastewater;
the flocculation precipitation process in the step 6) specifically comprises the following steps: adding mixed alkali into the clear liquid obtained in the step 5), adjusting the pH of the clear liquid to be alkalescent, and performing flocculating settling through weak alkali to obtain metal-containing sludge and salt-containing wastewater.
2. The method of claim 1, wherein: the method further comprises the following steps:
8) condensation and crystallization: cooling and condensing the ammonia-removal wastewater obtained in the step 7) to obtain crystal salt and clean water; clean water is circulated to the wet washing device (3); and/or
9) Metal recovery: and (3) carrying out a metal recovery process on the metal-containing sludge obtained in the step 6) to recover metals.
3. The method of claim 2, wherein: the high-alkali ammonia removal process specifically comprises the following steps: adding strong base into the salt-containing wastewater obtained in the step 6); adjusting the pH value of the salt-containing wastewater to 10-14, and separating and recovering ammonia to obtain an ammonia-containing byproduct and ammonia-removing wastewater; and/or
The condensation crystallization specifically comprises the following steps: adjusting the temperature of the ammonia removal wastewater obtained in the step 7) to low temperature, and condensing and crystallizing salt in the ammonia removal wastewater to obtain crystallized salt and clean water.
4. The method of claim 3, wherein: adjusting the pH value of the salt-containing wastewater to 10.5-13.5; and/or
The low temperature is 0-30 ℃.
5. The method of claim 4, wherein: adjusting the pH value of the salt-containing wastewater to 11-13; and/or
The low temperature is 5-25 ℃.
6. The method of claim 5, wherein: the separation adopts one or more methods of blowing to remove ammonia, membrane separation and evaporation to remove ammonia; and/or
The low temperature is 10-20 ℃.
7. The method of claim 6, wherein: the crystallization salt is one or more of sulfate, chloride and fluoride.
8. The method according to any one of claims 1-7, wherein: the oxidation in the step 6) adopts one or more of chemical oxidation, electrochemical oxidation, ultraviolet catalytic oxidation, air oxidation or medicament oxidation; and/or
Adjusting the pH of the clear solution to 7-10.
9. The method of claim 8, wherein: adjusting the pH of the clear solution to 7.2-9.
10. The method of claim 9, wherein: adjusting the pH of the clear solution to 7.5-8.5.
11. The method of claim 8, wherein: the mixed alkali is OH-containing-And CO3 2-A mixture of constituents, or containing OH-And HCO3 -A mixture of components.
12. The method according to claim 9 or 10, characterized in that: the mixed alkali is OH-containing-And CO3 2-A mixture of constituents, or containing OH-And HCO3 -A mixture of components.
13. The method of claim 11, wherein: the mixed alkali is a mixture of soluble hydroxide and soluble carbonate or a mixture of soluble hydroxide and soluble bicarbonate.
14. The method of claim 12, wherein: the mixed alkali is a mixture of soluble hydroxide and soluble carbonate or a mixture of soluble hydroxide and soluble bicarbonate.
15. The method according to claim 13 or 14, characterized in that: the mixed alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide, and is a mixture of one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
16. The method of any one of claims 1-7, 9-11, 13-14, wherein: in the step 2), screening the thermally regenerated activated carbon to obtain large-particle activated carbon and small-particle activated carbon; the large-particle activated carbon is returned to the flue gas adsorption device (1) in the step 1) for recycling; synthesizing the small-particle activated carbon into large-particle activated carbon through a carbon powder recycling process, and returning the large-particle activated carbon to the flue gas adsorption device (1) in the step 1) for recycling or serving as fuel; and/or
The carbon powder obtained in the step 5) is used for synthesizing large-particle activated carbon through a carbon powder recycling process and is returned to the flue gas adsorption device (1) in the step 1) for recycling or used as fuel.
17. The method of claim 8, wherein: in the step 2), screening the thermally regenerated activated carbon to obtain large-particle activated carbon and small-particle activated carbon; the large-particle activated carbon is returned to the flue gas adsorption device (1) in the step 1) for recycling; synthesizing the small-particle activated carbon into large-particle activated carbon through a carbon powder recycling process, and returning the large-particle activated carbon to the flue gas adsorption device (1) in the step 1) for recycling or serving as fuel; and/or
The carbon powder obtained in the step 5) is used for synthesizing large-particle activated carbon through a carbon powder recycling process and is returned to the flue gas adsorption device (1) in the step 1) for recycling or used as fuel.
18. The method of claim 16, wherein: the carbon powder recycling process adopts a mode of re-granulation, combustion or landfill.
19. The method of claim 17, wherein: the carbon powder recycling process adopts a mode of re-granulation, combustion or landfill.
20. The method of any one of claims 1-7, 9-11, 13-14, 17-19, wherein: step 4), a sulfur recycling process is carried out to obtain a sulfur-containing byproduct and a sulfur-containing tail gas; and/or
In the step 7), the strong base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
21. The method of claim 8, wherein: step 4), a sulfur recycling process is carried out to obtain a sulfur-containing byproduct and a sulfur-containing tail gas; and/or
In the step 7), the strong base is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
22. The method of claim 20, wherein: the sulfur-containing tail gas is conveyed to a flue gas conveying pipeline (L1) and recycled to the step 1).
23. The method of claim 21, wherein: the sulfur-containing tail gas is conveyed to a flue gas conveying pipeline (L1) and recycled to the step 1).
24. The method of any one of claims 1-7, 9-11, 13-14, 17-19, 21-23, wherein: the multi-pollutant flue gas is SO2Mixed flue gas consisting of one or more of NOx, dust, VOCs and heavy metals; and/or
The multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in steel, electric power, colored, petrochemical, chemical industry or building material industry.
25. The method of claim 8, wherein: the multi-pollutant flue gas is SO2Mixed flue gas consisting of one or more of NOx, dust, VOCs and heavy metals; and/or
The multi-pollutant flue gas is derived from complex gas containing sulfur dioxide generated in steel, electric power, colored, petrochemical, chemical industry or building material industry.
26. The method of claim 24, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%; the temperature of the multi-pollutant flue gas is 100-200 ℃.
27. The method of claim 25, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.01-1%; the temperature of the multi-pollutant flue gas is 100-200 ℃.
28. The method of claim 26 or 27, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.03-0.8%; the temperature of the multi-pollutant flue gas is 120-180 ℃.
29. The method of claim 28, wherein: the volume content of sulfur dioxide in the multi-pollutant flue gas is 0.05-0.5%; the temperature of the multi-pollutant flue gas is 130-160 ℃.
30. The method of any one of claims 1-7, 9-11, 13-14, 17-19, 21-23, 25-27, 29, wherein: the multi-pollutant flue gas in the step 1) is treated by adopting activated carbon, specifically, the activated carbon is used for adsorbing the multi-pollutant flue gas, and the activated carbon is used for adsorbing pollutants in the multi-pollutant flue gas; and/or
In the step 1), when the multi-pollutant flue gas contains NOx, ammonia gas is sprayed into the flue gas adsorption device (1).
31. The method of claim 8, wherein: the multi-pollutant flue gas in the step 1) is treated by adopting activated carbon, specifically, the activated carbon is used for adsorbing the multi-pollutant flue gas, and the activated carbon is used for adsorbing pollutants in the multi-pollutant flue gas; and/or
In the step 1), when the multi-pollutant flue gas contains NOx, ammonia gas is sprayed into the flue gas adsorption device (1).
32. The method of claim 30, wherein: the adsorption in the step 1) adopts cross-flow adsorption or countercurrent adsorption; and/or
In the step 1), the molar weight of the injected ammonia gas in unit time is 0.8-2 times of the molar weight of NOx contained in the flue gas flow in unit time.
33. The method of claim 31, wherein: the adsorption in the step 1) adopts cross-flow adsorption or countercurrent adsorption; and/or
In the step 1), the molar weight of the injected ammonia gas in unit time is 0.8-2 times of the molar weight of NOx contained in the flue gas flow in unit time.
34. The method of claim 32 or 33, wherein: in the step 1), the molar weight of the injected ammonia gas in unit time is 0.9-1.5 times of the molar weight of NOx contained in the flue gas flow in unit time.
35. The method of claim 34, wherein: in the step 1), the molar weight of the injected ammonia gas in unit time is 1.0-1.3 times of the molar weight of NOx contained in the flue gas flow in unit time.
36. The method of any one of claims 1-7, 9-11, 13-14, 17-19, 21-23, 25-27, 29, 31-33, 35, wherein: the thermal regeneration is to heat the activated carbon with saturated adsorption by adopting electric heating or hot air heating; and/or
The solution adopted by the wet washing is an acid solution.
37. The method of claim 8, wherein: the thermal regeneration is to heat the activated carbon with saturated adsorption by adopting electric heating or hot air heating; and/or
The solution adopted by the wet washing is an acid solution.
38. The method of claim 36, wherein: the temperature of thermal regeneration is 250-480 ℃; and/or
The pH value of the acidic solution is 0-7; in the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 10-100.
39. The method of claim 37, wherein: the temperature of thermal regeneration is 250-480 ℃; and/or
The pH value of the acidic solution is 0-7; in the wet washing process, the volume flow ratio of the SRG gas to the acidic solution is 1: 10-100.
40. The method of claim 38 or 39, wherein: the temperature of thermal regeneration is 300-450 ℃; and/or
The pH value of the acidic solution is 1-6; the volume flow ratio of the SRG gas to the acidic solution is 1: 20-80.
41. The method of claim 40, wherein: the temperature of thermal regeneration is 360-430 ℃; and/or
The pH value of the acidic solution is 2-5; the volume flow ratio of the SRG gas to the acidic solution is 1: 30-60.
42. The method of any one of claims 1-7, 9-11, 13-14, 17-19, 21-23, 25-27, 29, 31-33, 35, 37-39, 41, wherein: the sulfur recycling process specifically comprises the following steps: converting high-sulfur gas into sulfur-containing by-products, wherein the sulfur-containing by-products are sulfuric acid, sulfur and liquid SO2One or more of sulfite and sulfate; and/or
The acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants.
43. The method of claim 8, wherein: the sulfur recycling process specifically comprises the following steps: converting high-sulfur gas into sulfur-containing by-products, wherein the sulfur-containing by-products are sulfuric acid, sulfur and liquid SO2One or more of sulfite and sulfate; and/or
The acidic flue gas washing wastewater comprises one or more of suspended matters, metal ions, ammonia nitrogen, fluorine and chlorine and organic pollutants.
44. The method of claim 42, wherein: the sulfur recycling process specifically comprises the following steps: converting the high-sulfur gas into sulfuric acid; and/or
The metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
45. The method of claim 43, wherein: the sulfur recycling process specifically comprises the following steps: converting the high-sulfur gas into sulfuric acid; and/or
The metal ions are one or more of iron, copper, lead, calcium, zinc, cadmium, cobalt, nickel and aluminum.
46. The method of claim 42, wherein: the acid filtration is to remove suspended matters by utilizing the self gravity settling action or the filter interception action of the suspended matters, and the concentration of the suspended matters in the clear liquid after the acid filtration is 0-100 mg/L; and/or
And 8) further drying the crystal salt obtained in the step 8) by hot air, and then performing dust removal treatment.
47. The method of any one of claims 43-45, wherein: the acid filtration is to remove suspended matters by utilizing the self gravity settling action or the filter interception action of the suspended matters, and the concentration of the suspended matters in the clear liquid after the acid filtration is 0-100 mg/L; and/or
And 8) further drying the crystal salt obtained in the step 8) by hot air, and then performing dust removal treatment.
48. The method of claim 46, wherein: the concentration of suspended matters in the clear liquid after acidic filtration is 1-80 mg/L; and/or
And the dust removal treatment adopts dry dust removal.
49. The method of claim 47, wherein: the concentration of suspended matters in the clear liquid after acidic filtration is 1-80 mg/L; and/or
And the dust removal treatment adopts dry dust removal.
50. The method of claim 48 or 49, wherein: the concentration of suspended matters in the clear liquid after acidic filtration is 2-50 mg/L; and/or
The dust removal treatment is one of electric dust removal, cloth bag dust removal and ceramic dust removal.
51. The method of claim 50, wherein: the dust removal treatment is cloth bag dust removal.
52. An apparatus for the method according to any one of claims 1 to 51, comprising a flue gas conveying pipeline (L1), a flue gas adsorption device (1), an activated carbon thermal regeneration device (2), a wet scrubbing device (3), a sulfur recycling device (4), an acid filtration device (5), an oxidation device (6) and a flocculation precipitation device (7); the multi-pollutant flue gas is conveyed to a flue gas adsorption device (1) through a flue gas conveying pipeline (L1), an activated carbon outlet of the flue gas adsorption device (1) is connected to an activated carbon thermal regeneration device (2) through a conveying device, an SRG gas outlet of the activated carbon thermal regeneration device (2) is connected to a wet washing device (3) through a pipeline, a high-sulfur gas outlet of the wet washing device (3) is connected to a sulfur resource device (4), a wastewater outlet of the wet washing device (3) is connected to an acid filtering device (5), a liquid outlet of the acid filtering device (5) is connected to an oxidizing device (6), and an outlet of the oxidizing device (6) is connected to a flocculation precipitation device (7).
53. The apparatus of claim 52, wherein: the device also comprises a high-alkali ammonia removal device (8) and a condensation crystallization device (9); a liquid outlet of the flocculation precipitation device (7) is connected to a high-alkali ammonia removal device (8), a liquid outlet of the high-alkali ammonia removal device (8) is connected to a condensation crystallization device (9), and a clean water outlet of the condensation crystallization device (9) is connected to the wet washing device (3); and/or
The device also comprises a screening device (10) and a carbon powder recycling device (11); an activated carbon outlet of the activated carbon thermal regeneration device (2) is connected to the screening device (10), a large-particle activated carbon outlet of the screening device (10) is connected to the flue gas adsorption device (1), a small-particle activated carbon outlet of the screening device (10) and a solid outlet of the acid filtering device (5) are connected to the carbon powder recycling device (11), and a discharge hole of the carbon powder recycling device (11) is connected to the flue gas adsorption device (1).
54. The apparatus of claim 52 or 53, wherein: the apparatus also includes a metal recovery device (12); the solid outlet of the flocculation precipitation device (7) is connected to a metal recovery device (12); and/or
The sulfur-containing tail gas outlet of the sulfur recycling device (4) is connected to the flue gas conveying pipeline (L1) or the flue gas adsorption device (1).
55. The apparatus of claim 54, wherein: the flue gas adsorption device (1) is an adsorption tower, and the activated carbon thermal regeneration device (2) is an analytical tower.
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