CN107617335A - The hydrogen sulfide cleaning system and method for a kind of microwave-excitation Magneto separate catalyst - Google Patents

The hydrogen sulfide cleaning system and method for a kind of microwave-excitation Magneto separate catalyst Download PDF

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CN107617335A
CN107617335A CN201710914004.4A CN201710914004A CN107617335A CN 107617335 A CN107617335 A CN 107617335A CN 201710914004 A CN201710914004 A CN 201710914004A CN 107617335 A CN107617335 A CN 107617335A
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microwave
hydrogen sulfide
catalyst
tower
sulfuric acid
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CN107617335B (en
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刘杨先
王燕
王智化
张军
赵亮
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Jiangsu University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals

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Abstract

The invention provides a kind of hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst and method, after the hydrogen sulfide containing flue gas removing dust cooling from emission source, uses a part of hydrogen sulfide of ozone pre-oxidation in flue as gaseous sulfuric acid.Microwave-excitation can Magnetic Isolation catalyst to activate peroxide in microwave atomizing reactor to produce hydroxyl and potentiometric titrations by remaining Oxidation of Hydrogen Sulfide be gaseous sulfuric acid.Caused gaseous sulfuric acid is produced sulfuric acid solution after the spray column washing absorption of afterbody.Caused sulfuric acid solution initially enters progress magnetic separation reclaiming in catalyst magnetic separation tower in spray column.Sulfuric acid solution enters neutralizing tower and produces ammonium sulfate, finally enters evaporative crystallization knockout tower.Using acquisition solid-state ammonium sulfate fertilizer after high-temperature flue gas afterheat utilizing system evaporative crystallization.The system can realize 100% removing of hydrogen sulfide, and subtractive process non-secondary pollution, have wide market application foreground.

Description

The hydrogen sulfide cleaning system and method for a kind of microwave-excitation Magneto separate catalyst
Technical field
The present invention relates to.The present invention relates to filed of flue gas purification, and in particular to one kind is based on Chou Yang ﹑ hydroxyls and sulfate radical certainly By the system and method for the sulfureous in flue gas hydrogen purification of base advanced oxidation.
Background technology
Hydrogen sulfide (H2S) it is a kind of high irritating hypertoxic gas.Under aerobic and wet heat condition, hydrogen sulfide can not only draw Equipment corrosion and catalyst poisoning are played, can also serious threat personal safety.With the fast development of economy and people's environmental consciousness Raising, hydrogen sulfide stripping problem has been to be concerned by more and more people in industrial waste gas.Country has also formulated corresponding method simultaneously Strict limitation has been made in discharge of the Laws ＆ Regulations to hydrogen sulfide.The efficient removal technology of research and development hydrogen sulfide turns into countries in the world The hot issue of scientific and technical personnel's concern.In the past few decades, domestic and international researcher is to hydrogen sulfide stripping problem in waste gas Make substantial amounts of research and develop many hydrogen sulfide stripping methods.According to the dry and wet form of subtractive process, hydrogen sulfide in waste gas Removal methods can substantially be divided into the major class of dry and wet two.Dry method is the reproducibility and combustibility using hydrogen sulfide, with fixation Oxidant or absorbent come desulfurization or directly burning.This method includes Claus method, non-renewable ADSORPTION IN A FIXED BED method, film point From method, sieve method, pressure-variable adsorption (PSA) method, low temperature processing etc..Mainly active charcoal, the oxidation of desulfurizer therefor, catalyst The resource such as iron, zinc oxide, manganese dioxide and bauxite etc., general recyclable sulphur, sulfur dioxide, sulfuric acid and sulfate.Dry method Removing process efficiency is typically adapted to gas compared with high but the deficiencies such as equipment investment is big, desulfurizing agent needs super regeneration and sulfur capacity is low be present The fine desulfurization of body.Although Claus method can be used for the removing of high-concentration hydrogen sulfide, but the deficiencies of removal efficiency difference be present.
Wet method removing sulfuldioxide can be divided into chemical absorption method, Physical Absorption method, physical chemistry absorption process according to removal mechanism And wet oxidation process.Chemical absorption method is to remove hydrogen sulfide using the reversible reaction occurred between hydrogen sulfide and chemical solvent. Common method includes amine method, hot carbonate method and ammonia process etc..Physical Absorption method is to be dissolved using different component in specific solvent Spend difference and remove hydrogen sulfide, then separate out hydrogen sulfide by being depressured the measures such as flash distillation and absorbent regeneration.Conventional physics is molten Agent method includes low-temp methanol method, polyglycol dimethyl ether process, N methylpyrrolidone process etc..Physical chemistry absorption process is by physics Solvent and chemical solvent mixing, make it have the characteristic of two kinds of solvents concurrently, its Typical Representative is sulfone amine method.Wet oxidation process refers to adopt By Oxidation of Hydrogen Sulfide it is that elemental sulfur or sulfuric acid solution are reclaimed with oxidant.According to the difference of oxidation mechanism, wet oxidation process It can be divided mainly into iron-based, vanadium base etc. as the catalytic oxidation of representative and with direct oxygen that hydrogen peroxide, potassium permanganate etc. are representative Change method.At present, hydrogen sulfide wet method removing process is there is also many problems, such as the various organic absorbents or oxidant newly synthesized Jia Ge Gao ﹑ performance Bu Wen, which are Dinged, ﹑ or even also has toxicity.The oxidant reaction such as potassium permanganate process can produce the accessory substance of complexity, Cause product utilization difficult.The oxidants such as hydrogen peroxide are although environmental clean, but oxidation efficiency is low, cause subtractive process not meet Increasingly strict environmental requirement.
Chinese patent (ZL201210075896.0) proposes hydrogen peroxide oxidation and absorbed to be taken off with the hydrogen sulfide of afterbody UF membrane Except method and technique, but the dioxygen water absorbent oxidability difference ﹑ removal efficiencies used in this method are low, can only remove low concentration sulphur Change hydrogen, and the film of afterbody causes the high ﹑ system reliabilities of system operation expense poor easily by dioxygen aqueous corrosion.
Chinese patent (ZL 201310490922.0) proposes one kind and absorbs hydrogen sulfide using sodium carbonate, and with oxygen again Raw removal methods and technique, but this method complex process, and the sodium acid carbonate accessory substance containing impurity caused by reaction can not Recycling.Chinese patent (ZL201210410079.6) proposes a kind of using iron system scavenger catalytic decomposition hydrogen sulfide Method and technique, but the scavenger preparation method that this method proposes is extremely complex, and absorbent stability is not high.Chinese patent (ZL201310648205.6) a kind of method that hydrogen sulfide is captured using ionic liquid, but the ionic liquid that this method uses are proposed Body synthetic method is extremely complex, and application cost is high, and absorbent properties are unstable, and product separation is difficult.
Chinese patent (ZL201510191673.4) proposes a kind of hydrogen sulfide stripping method based on photocatalysis spray, but The patent difference maximum with the present invention is that it employs ultraviolet light as excitaton source.But it is known that ultraviolet light is in water The penetration range neutralized in solid is extremely short.There is relevant report to show, even in pure water, 254nm short wave ultraviolet lights have Effect spread distance also only has several centimetres, and ultraviolet light can only react in solid superficial face, and this can cause removing means to be difficult to Maximization.In addition, the transmission that the impurity such as particulate matter can seriously hinder ultraviolet light in actual coal-fired flue-gas be present, and then influence photochemical Learn the safe and highly efficient operation of removing system.Therefore, the serious commercial Application for constraining photochemistry removing system of above deficiency.
In summary, there is presently no a kind of Wen to determine Ke Kao ﹑ economical and effectives, and is suitable for middle low concentration gas hydrogen sulfide and takes off The technique removed.Therefore, while existing removing sulfuldioxide is improved, the new waste gas hydrogen sulfide stripping skill of active development economical and efficient Art has most important theories meaning and realistic meaning.
The content of the invention
For Shortcomings in the prior art, the invention provides a kind of vulcanization of microwave-excitation Magneto separate catalyst Hydrogen purification system and method, can Magnetic Isolation catalyst peroxynitrite decomposition using the microwave-excitation that can effectively penetrate solid and liquid Compound produces the hydroxyl or potentiometric titrations of strong oxidizing property, the hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst 100% removal efficiency of hydrogen sulfide can be realized, disclosure satisfy that the coal-burning boiler newly put into effect of country and the ultra-clean discharge of kiln waste gas will Ask, there is the wide market development and application prospect.Meanwhile present invention process is simple, system it is reliable, application cost compared with It is low.
To realize object above, the embodiment that the present invention uses is as follows：
A kind of hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst, it is characterised in that：It is main to include successively Chu Chen Qi ﹑ Leng Que Qi ﹑ ozone supplieds Xi Tong ﹑ microwave atomizings anti-Ying Qi ﹑ spray columns and blower fan on flue, the microwave spray Mist inside reactor is divided into several microwave magnetron installing zones and solution spray reaction area by quartz glass dividing plate, described micro- Several microwave magnetrons are installed in ripple magnetron installing zone, multiple atomizers are set in the solution spray reaction area, it is described Atomizer is connected with solution/catalyst make-up tower, is additionally provided between the atomizer and solution/catalyst make-up tower molten Liquid pump；Each solution spray reaction area carries exhanst gas outlet and smoke inlet, and the smoke inlet and exhanst gas outlet pass through respectively Connected by flue gas main entrance, flue gas general export with flue；Each microwave magnetron installing zone is respectively provided with Leng, and but Kong gas Ru Kou ﹑ are cooled down Air outlet slit, Leng are but connected the outlet of Kong gas Ru Kou ﹑ cooling airs with cooling air main entrance, cooling air general export respectively；
The spray column is also successively with catalyst magnetic separation tower ﹑ mercury point from tower ﹑ and tower ﹑ evaporative crystallization knockout tower phases Even, set fume afterheat to utilize bypass line drainage portion flue gas on the flue between the deduster and cooler, utilize cigarette The waste heat of gas provides heat for evaporative crystallization knockout tower；The catalyst magnetic separation tower also with solution/catalyst make-up tower phase Even.
Further, the horizontal and vertical section of the microwave atomizing reactor is rectangle, solution spray reaction area with Arranged for interval, multiple solution spray reaction areas are parallel relationship to microwave magnetron installing zone successively.
Further, the optimal overall width W of microwave atomizing reactor is between 0.2m-10m；Microwave atomizing reactor Optimal total length L is between 0.2m-9m；The optimal overall height H of microwave atomizing reactor is between 0.2m-9m.
Further, the optimum width b in each solution spray reaction area is between 0.1m-1.5m；Microwave magnetron it Between optimal lateral spacing a between 0.1m-1.2m；The optimal lateral arrangement spacing of atomizer is 2a, is longitudinally arranged optimal Spacing is 1.5a.
Further, the optimum distance J between ozone adding mouth and microwave atomizing reactor is 0.1m-8m.
The hydrogen sulfide purification method of microwave-excitation Magneto separate catalyst, it is characterised in that comprise the following steps：
Step 1：First after the hydrogen sulfide containing flue gas removing dust cooling in self-discharging in future source, using ozone in flue it is pre- A part of hydrogen sulfide of initial oxidation is gaseous sulfuric acid；
Step 2：Flue injection peroxide, catalyst, microwave-excitation can Magnetic Isolation catalyst it is anti-in microwave atomizing It is gaseous sulfuric acid to answer and peroxide generation hydroxyl and potentiometric titrations are activated in device by remaining Oxidation of Hydrogen Sulfide；
Step 3：Caused gaseous sulfuric acid is produced sulfuric acid solution after the spray column washing absorption of afterbody.Produced in spray column Raw sulfuric acid solution initially enters progress magnetic separation reclaiming in catalyst magnetic separation tower；
Step 4：Sulfuric acid solution enters neutralizing tower and produces ammonium sulfate, finally enters evaporative crystallization knockout tower.Using height Solid-state ammonium sulfate fertilizer is obtained after warm smoke waste heat utilization system evaporative crystallization.
Further, the optimal of ozone adds concentration between 40ppm-600ppm；Temperature in microwave atomizing reactor At 30-250 DEG C, effective liquid-gas ratio of peroxide solutions and flue gas is 0.1-5.0L/m for control3, the valid density of peroxide Between 0.01mol/L-2.0mol/L, the pH of solution is between 0.2-10.8, the atomization droplets diameter of atomizer ejection No more than 100 microns, the microwave irradiation power density in microwave atomizing reactor is 20W/m3-1600W/m3, microwave irradiation power Density refers to the ratio of the power output of microwave and reactor void tower volume in microwave atomizing reactor, and unit is watt/cubic metre.
Further, can the dosage of Magnetic Isolation catalyst added by every cubic metre of microwave atomizing reactor volume 0.2-8kg, the content of sulfureous in flue gas hydrogen are not higher than 20000mg/m3。
Further, it is described can Magnetic Isolation catalyst include di-iron trioxide (Fe2O3) ﹑ ferroso-ferric oxides (Fe3O4) the metal composite oxide that ﹑ and iron Yu Tong ﹑ Gu ﹑ Meng ﹑ zinc are formed；Described peroxide is Shuan Yang Shui ﹑ persulfuric acid Mixing more than one or both of An ﹑ permonosulphuric acid hydrogen potassium Fu He Yan ﹑ sodium peroxydisulfates and potassium peroxydisulfate.
Advantages of the present invention and remarkable result：
Microwave activation of the present invention removes system, and compared with ultraviolet light, microwave can effectively penetrate solid and liquid, and More, the microwave activation free radical system activation than UV-activated system longer than ultraviolet light of the penetration range of microwave in the solution Effect is good.Using can effectively penetrate solid and liquid microwave-excitation can Magnetic Isolation catalyst peroxynitrite decomposition compound produce it is strong The hydroxyl or potentiometric titrations of oxidisability, the hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst can realize vulcanization 100% removal efficiency of hydrogen, the requirement of the national coal-burning boiler newly put into effect and the ultra-clean discharge of kiln waste gas is disclosure satisfy that, is had wide The market development and application prospect.In addition, microwave technology has obtained large-scale application in industry and daily life, have very Good engineering uses and practical experience.Therefore the operational reliability of the system is higher, technology more mature and reliable.
Meanwhile present invention process is simple, subtractive process is reliable and stable, and application cost is relatively low.Caused reaction product sulfuric acid Ammonium is a kind of good agricultural fertilizer, therefore whole subtractive process does not have secondary pollution.System it is reliable, feasible system Continuous operation.
Brief description of the drawings
Fig. 1 is the determining free radicals that microwave-excitation can be in Magnetic Isolation catalyst peroxynitrite decomposition compound system：(a) mistake One potassium acid sulfate complex salt, (b) hydrogen peroxide, (c) persulfate, spectrum peak represent potentiometric titrations and hydroxyl radical free radical
Fig. 2 is the process chart of present system
Fig. 3 is the top view of the key devices such as the atomization nozzle of microwave atomizing reactor and microwave magnetron.
Fig. 4 is the front view of the key devices such as the atomization nozzle of microwave atomizing reactor and microwave magnetron.
In figure：
1- dedusters, 2- coolers, 3- fume afterheats utilize bypass line, 4- microwave atomizing reactors, 5- spray columns, 6- Blower fan, 7- catalyst magnetic separation towers, 8- mercury knockout towers, 9- neutralizing towers, 10- evaporative crystallization knockout towers, 11- solution/catalyst Supplement tower, 12- solution pumps, 13- ozone supplied systems, 14- atomizers, 15- microwave magnetrons, 16- quartz glass dividing plates.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is simultaneously Not limited to this.
After hydrogen sulfide containing flue gas removing dust cooling from emission source, using ozone, pre-oxidation is a part of in flue Hydrogen sulfide is gaseous sulfuric acid.Microwave-excitation can Magnetic Isolation catalyst activated in microwave atomizing reactor 4 peroxide generation Remaining Oxidation of Hydrogen Sulfide is gaseous sulfuric acid by hydroxyl and potentiometric titrations.Caused gaseous sulfuric acid is by the spray column 5 of afterbody Sulfuric acid solution is produced after washing absorption.Caused sulfuric acid solution initially enters in spray column 5 enters in catalyst magnetic separation tower 7 Row magnetic separation reclaiming.Sulfuric acid solution enters neutralizing tower 9 and produces ammonium sulfate, finally enters evaporative crystallization knockout tower 10.Using acquisition solid-state ammonium sulfate fertilizer after high-temperature flue gas afterheat utilizing system evaporative crystallization.The system can realize hydrogen sulfide 100% removing, and subtractive process non-secondary pollution has wide market application foreground.
The course of reaction general principle of the present invention：
1st, ozone has very strong oxidisability, therefore adds in flue the oxygen that following reaction equation (1) can occur after ozone Change reaction.By the pre-oxidation, the H in waste gas2S can be oxidized to gaseous sulfuric acid：
4O3+H2S→H2SO4+4O2 (1)
2nd, microwave (MW) excite can Magnetic Isolation catalyst (Catalyst) peroxide (dioxygen can effectively be catalytically decomposed Shui ﹑ potassium hydrogen persulfate composite salts and persulfate) and ozone produce high activity potentiometric titrations and hydroxyl radical free radical.This Outside, the ozone of flue injection can also trigger chain reaction to produce hydroxyl radical free radical with hydrogen peroxide.Specific course of reaction can pass through Equation below (2)-(8) represent.Produced as shown in figure 1, being successfully measured in removing system using electron spin resonance kaleidophon Raw potentiometric titrations and hydroxyl radical free radical, so as to confirm above-described general principle.
2O3+H2O2→2·OH+3O2 (7)
3rd, (2)-potentiometric titrations and the hydroxyl radical free radical caused by (8) of reaction more than has superpower oxidisability, can By the H in waste gas2S is ultimately oxidized as gaseous sulfuric acid.Available following reaction (9)-(10) of detailed process represent.
2·OH+H2S→H2SO4+H2O (9)
4th, more than oxidation caused by gas sulfuric acid can by after the washing absorption of spray column 5 of afterbody produce can Magnetic Isolation urge The mixed solution of agent and sulfuric acid.In order to reuse catalyst and realize that the resourcebility of product utilizes and avoided secondary dirt Dye, mixed solution carry out magnetic separation with recovery and reusing and recycling catalyst in catalyst magnetic separation tower 7.Remaining sulphur solution Ammonium sulfate is produced into neutralizing tower 9.Ammonium sulfate finally enters evaporative crystallization knockout tower 10.Using high-temperature flue gas waste heat Using solid-state ammonium sulfate and ammonium nitrate fertilizer is obtained after system evaporative crystallization, so as to realize that the resourcebility of product utilizes, prevent Secondary pollution.
As shown in Fig. 2 the hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst of the present invention, main bag Include the ﹑ spray columns 5 of 1 13 ﹑ microwave atomizings reactor of ﹑ Leng Que Qi ﹑ ozone supplieds systems of deduster 4 and blower fan successively on flue 6, several installing zones of microwave magnetron 15 and solution are divided into by quartz glass dividing plate 16 inside the microwave atomizing reactor 4 Spray reaction area, the several microwave magnetrons 15 of installation in the installing zone of microwave magnetron 15, in the solution spray reaction area Multiple atomizers 14 are set, the atomizer 14 is connected with solution/catalyst make-up tower 11, the atomizer 14 with it is molten Solution pump 12 is additionally provided between liquid/catalyst make-up tower 11；Each solution spray reaction area carries exhanst gas outlet and flue gas Entrance, the smoke inlet and exhanst gas outlet connect via flue gas main entrance, flue gas general export with flue respectively；Each microwave magnetic The installing zone of keyholed back plate 15 be respectively provided with Leng but Kong gas Ru Kou ﹑ cooling airs export, Leng but Kong gas Ru Kou ﹑ cooling airs outlet respectively with it is cold But air main entrance, the connection of cooling air general export；The spray column 5 also successively with the ﹑ mercury knockout towers of catalyst magnetic separation tower 7 The ﹑ evaporative crystallizations knockout tower 10 of 8 ﹑ neutralizing towers 9 is connected, and fume afterheat profit is set on the flue between the deduster 1 and cooler 2 With the drainage portion flue gas of bypass line 3, heat is provided for evaporative crystallization knockout tower 10 using the waste heat of flue gas；The catalyst magnetic Power knockout tower 7 is also connected with solution/catalyst make-up tower 11.
As shown in Figure 3, Figure 4, the horizontal and vertical section of the microwave atomizing reactor 4 is rectangle, and solution spraying is anti- Answering area, arranged for interval, multiple solution spray reaction areas are parallel relationship successively with the installing zone of microwave magnetron 15.Microwave atomizing is anti- Answer in device 4, the width b in each solution spray reaction area is between 0.1m-1.5m；The overall width W positions of microwave atomizing reactor 4 Between 0.2m-10m；Horizontal spacing a between microwave magnetron 15 is between 0.1m-1.2m；Microwave atomizing reactor 4 it is total Length L is between 0.2m-9m；The overall height H of microwave atomizing reactor 4 is between 0.2m-9m.The transverse direction of atomizer 14 Arrangement spacing is 2a, and it is 1.5a to be longitudinally arranged spacing.Optimum distance J between ozone adding mouth and microwave atomizing reactor 4 is 0.1m-8m.The optimal of ozone adds concentration between 40ppm-600ppm.Temperature in microwave atomizing reactor 4 should control 30-250 DEG C, effective liquid-gas ratio of peroxide solutions and flue gas is 0.1-5.0L/m3, the valid density of peroxide is Between 0.01mol/L-2.0mol/L, the pH of solution is between 0.2-10.8, the atomization droplets diameter of the ejection of atomizer 14 No more than 100 microns, the microwave irradiation power density in microwave atomizing reactor 4 is 20W/m3-1600W/m3, microwave radiation work( Rate density refers to the ratio of the power output of microwave and reactor void tower volume in microwave atomizing reactor 4, and unit is watt/cube Rice.
Can the dosage of Magnetic Isolation catalyst add 0.2-8kg, cigarette by every cubic metre of the volume of microwave atomizing reactor 4 The content of hydrogen sulfide is respectively no higher than 50000ppm in gas.It is described can Magnetic Isolation catalyst include di-iron trioxide (Fe2O3) ﹑ ferroso-ferric oxides (Fe3O4) the metal composite oxide that ﹑ and iron Yu Tong ﹑ Gu ﹑ Meng ﹑ zinc are formed, such as CoFe2O4﹑ CuFe2O4﹑ MnFe2O4﹑ ZnFe2O4And the more metal composites formed by two or more oxide-metal combinations described above are catalyzed Agent.Described peroxide is in Shuan Yang Shui ﹑ Guo Liu Suan An ﹑ permonosulphuric acid hydrogen potassium Fu He Yan ﹑ sodium peroxydisulfates and potassium peroxydisulfate One or more kinds of mixing.
Embodiment 1.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, ozone concentration 80ppm, potassium hydrogen peroxymonosulfate The molar concentration of complex salt is 0.1mol/L, pH value of solution 3.9, catalyst CoFe2O4Dosage be every cubic metre of 0.2kg, it is micro- Wave radiation power density is 200W/m3, liquid-gas ratio 2L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 62.2%.
Embodiment 3.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, ozone concentration 80ppm, potassium hydrogen peroxymonosulfate The molar concentration of complex salt is 0.2mol/L, pH value of solution 3.9, catalyst CoFe2O4Dosage be every cubic metre of 0.4kg, it is micro- Wave radiation power density is 200W/m3, liquid-gas ratio 2L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 87.5%.
Embodiment 3.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, ozone concentration 80ppm, potassium hydrogen peroxymonosulfate The molar concentration of complex salt is 0.2mol/L, pH value of solution 3.9, catalyst CoFe2O4Dosage be every cubic metre of 0.4kg, it is micro- Wave radiation power density is 500W/m3, liquid-gas ratio 3L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 100%.
Embodiment 4.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, and ozone concentration 100ppm, ammonium persulfate rubs Your concentration is 0.1mol/L, pH value of solution 3.9, catalyst CuFe2O4Dosage be every cubic metre of 0.2kg, microwave irradiation power Density is 200W/m3, liquid-gas ratio 2L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 69.9%.
Embodiment 5.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, and ozone concentration 100ppm, ammonium persulfate rubs Your concentration is 0.2mol/L, pH value of solution 3.9, catalyst CuFe2O4Dosage be every cubic metre of 0.4kg, microwave irradiation power Density is 200W/m3, liquid-gas ratio 2L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 93.4%.
Embodiment 6.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, and ozone concentration 100ppm, ammonium persulfate rubs Your concentration is 0.2mol/L, pH value of solution 3.9, catalyst CuFe2O4Dosage be every cubic metre of 0.4kg, microwave irradiation power Density is 500W/m3, liquid-gas ratio 3L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 100%.
Embodiment 7.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, and ozone concentration 100ppm, ammonium persulfate rubs Your concentration is 0.2mol/L, pH value of solution 3.9, catalyst MnFe2O4Dosage be every cubic metre of 0.2kg, microwave irradiation power Density is 200W/m3, liquid-gas ratio 2L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 49.3%.
Embodiment 8.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, and ozone concentration 100ppm, ammonium persulfate rubs Your concentration is 0.3mol/L, pH value of solution 3.9, catalyst MnFe2O4Dosage be every cubic metre of 0.4kg, microwave irradiation power Density is 200W/m3, liquid-gas ratio 2L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 73.1%.
Embodiment 9.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, and ozone concentration 100ppm, ammonium persulfate rubs Your concentration is 0.5mol/L, pH value of solution 3.9, catalyst MnFe2O4Dosage be every cubic metre of 0.4kg, microwave irradiation power Density is 500W/m3, liquid-gas ratio 3L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 93.8%.
Embodiment 10.
Sulfureous in flue gas hydrogen concentration is 800ppm, and flue-gas temperature is 40 DEG C, and ozone concentration 100ppm, ammonium persulfate rubs Your concentration is 0.8mol/L, pH value of solution 3.9, catalyst MnFe2O4Dosage be every cubic metre of 0.4kg, microwave irradiation power Density is 800W/m3, liquid-gas ratio 3L/m3.Pilot run is：The efficiency of removing of hydrogen sulfide is 100%.
Comprehensive Correlation by above example understands that embodiment 3,6 and 10 has optimal removal effect, removal efficiency Reach 100%, can be consulted and used as most preferred embodiment.
The embodiment is preferred embodiment of the invention, but the present invention is not limited to above-mentioned embodiment, not Away from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace Or modification belongs to protection scope of the present invention.

Claims (9)

  1. A kind of 1. hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst, it is characterised in that：It is main to include filling successively On flue deduster (1) ﹑ coolers (2) ﹑ ozone supplieds systems (13) ﹑ microwave atomizings reactors (4) ﹑ spray columns (5) and Blower fan (6), the microwave atomizing reactor (4) is internal to be divided into several microwave magnetrons (15) by quartz glass dividing plate (16) Installing zone and solution spray reaction area, the interior several microwave magnetrons (15) of installation of microwave magnetron (15) installing zone are described Multiple atomizers (14), the atomizer (14) and solution/catalyst make-up tower (11) are set in solution spray reaction area It is connected, solution pump (12) is additionally provided between the atomizer (14) and solution/catalyst make-up tower (11)；Each solution spray Mist reaction zone carries exhanst gas outlet and smoke inlet, and the smoke inlet and exhanst gas outlet are respectively via flue gas main entrance, cigarette Gas general export connects with flue；Each microwave magnetron (15) installing zone is respectively provided with Leng, and but Kong gas Ru Kou ﹑ cooling airs export, cold But Kong gas Ru Kou ﹑ cooling airs outlet connects with cooling air main entrance, cooling air general export respectively；
    Also (((9) ﹑ evaporative crystallizations divide 8) ﹑ neutralizing towers 7) ﹑ mercury knockout towers the spray column (5) with catalyst magnetic separation tower successively It is connected from tower (10), sets fume afterheat to utilize bypass line (3) on the flue between the deduster (1) and cooler (2) Drainage portion flue gas, heat is provided for evaporative crystallization knockout tower (10) using the waste heat of flue gas；The catalyst magnetic separation tower (7) also it is connected with solution/catalyst make-up tower (11).
  2. 2. the hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst according to claim 1, it is characterised in that： The horizontal and vertical section of the microwave atomizing reactor (4) is rectangle, solution spray reaction area and microwave magnetron (15) Arranged for interval, multiple solution spray reaction areas are parallel relationship to installing zone successively.
  3. 3. the hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst according to claim 1, it is characterised in that： The optimal overall width W of microwave atomizing reactor (4) is between 0.2m-10m；The optimal total length L of microwave atomizing reactor (4) Between 0.2m-9m；The optimal overall height H of microwave atomizing reactor (4) is between 0.2m-9m.
  4. 4. the hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst according to claim 1, it is characterised in that： The optimum width b in each solution spray reaction area is between 0.1m-1.5m；Between optimal lateral between microwave magnetron (15) Away from a between 0.1m-1.2m；The optimal lateral arrangement spacing of atomizer (14) is 2a, and it is 1.5a to be longitudinally arranged optimal spacing.
  5. 5. the hydrogen sulfide cleaning system of microwave-excitation Magneto separate catalyst according to claim 1, it is characterised in that： Optimum distance J between ozone adding mouth and microwave atomizing reactor (4) is 0.1m-8m.
  6. 6. the hydrogen sulfide purification method of microwave-excitation Magneto separate catalyst, it is characterised in that comprise the following steps：
    Step 1：First self-discharging in future source hydrogen sulfide containing flue gas removing dust cooling after, using ozone in flue advance oxygen It is gaseous sulfuric acid to change a part of hydrogen sulfide；
    Step 2：Flue injection peroxide, catalyst, microwave-excitation can Magnetic Isolation catalyst in microwave atomizing reactor (4) it is gaseous sulfuric acid that activation peroxide, which produces hydroxyl and potentiometric titrations by remaining Oxidation of Hydrogen Sulfide, in；
    Step 3：Caused gaseous sulfuric acid is produced sulfuric acid solution after spray column (5) washing absorption of afterbody.In spray column (5) Caused sulfuric acid solution, which initially enters, carries out magnetic separation reclaiming in catalyst magnetic separation tower (7)；
    Step 4：Sulfuric acid solution enters neutralizing tower (9) and produces ammonium sulfate, finally enters evaporative crystallization knockout tower (10).Using Solid-state ammonium sulfate fertilizer is obtained after high-temperature flue gas afterheat utilizing system evaporative crystallization.
  7. 7. the hydrogen sulfide purification method of microwave-excitation Magneto separate catalyst according to claim 6, it is characterised in that： The optimal of ozone adds concentration between 40ppm-600ppm；Temperature control in microwave atomizing reactor (4) at 30-250 DEG C, Effective liquid-gas ratio of peroxide solutions and flue gas is 0.1-5.0L/m3, the valid density of peroxide is 0.01mol/L- Between 2.0mol/L, for the pH of solution between 0.2-10.8, the atomization droplets diameter that atomizer (14) sprays is not more than 100 Micron, the microwave irradiation power density in microwave atomizing reactor (4) is 20W/m3-1600W/m3, microwave irradiation power density is Refer to the power output of microwave atomizing reactor (4) interior microwave and the ratio of reactor void tower volume, unit is watt/cubic metre.
  8. 8. the hydrogen sulfide purification method of microwave-excitation Magneto separate catalyst according to claim 6, it is characterised in that： Can the dosage of Magnetic Isolation catalyst add 0.2-8kg, sulfureous in flue gas by every cubic metre of microwave atomizing reactor (4) volume The content for changing hydrogen is not higher than 20000mg/m3。
  9. 9. the hydrogen sulfide purification method of microwave-excitation Magneto separate catalyst according to claim 6, it is characterised in that： It is described can Magnetic Isolation catalyst include di-iron trioxide (Fe2O3) ﹑ ferroso-ferric oxides (Fe3O4) ﹑ and iron Yu Tong ﹑ Gu ﹑ The metal composite oxide that Meng ﹑ zinc is formed；Described peroxide is Shuan Yang Shui ﹑ Guo Liu Suan An ﹑ permonosulphuric acid hydrogen potassium Fu He Yan ﹑ Mixing more than one or both of sodium peroxydisulfate and potassium peroxydisulfate.
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Publication number Priority date Publication date Assignee Title
US20060252630A1 (en) * 2005-01-31 2006-11-09 Fanson Paul T Microwave assisted desulfurization of nitrogen oxide storage reduction catalysts
CN203725007U (en) * 2014-01-27 2014-07-23 上海玖富环保科技有限公司 Exhaust gas microwave catalytic purification device
CN104857825A (en) * 2015-04-30 2015-08-26 江苏大学 Hydrogen sulfide removing system based on photochemistry atomizing bed
CN104923061A (en) * 2015-04-21 2015-09-23 江苏大学 Hydrogen sulfide removal method based on photochemical free radicals
CN104923072A (en) * 2015-04-21 2015-09-23 江苏大学 Hydrogen sulfide removal method based on photocatalytic spraying

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060252630A1 (en) * 2005-01-31 2006-11-09 Fanson Paul T Microwave assisted desulfurization of nitrogen oxide storage reduction catalysts
CN203725007U (en) * 2014-01-27 2014-07-23 上海玖富环保科技有限公司 Exhaust gas microwave catalytic purification device
CN104923061A (en) * 2015-04-21 2015-09-23 江苏大学 Hydrogen sulfide removal method based on photochemical free radicals
CN104923072A (en) * 2015-04-21 2015-09-23 江苏大学 Hydrogen sulfide removal method based on photocatalytic spraying
CN104857825A (en) * 2015-04-30 2015-08-26 江苏大学 Hydrogen sulfide removing system based on photochemistry atomizing bed

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