CN116462160A - By flue gas SO 2 Method and system for preparing steady-state chlorine dioxide for raw materials - Google Patents
By flue gas SO 2 Method and system for preparing steady-state chlorine dioxide for raw materials Download PDFInfo
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- CN116462160A CN116462160A CN202310319768.4A CN202310319768A CN116462160A CN 116462160 A CN116462160 A CN 116462160A CN 202310319768 A CN202310319768 A CN 202310319768A CN 116462160 A CN116462160 A CN 116462160A
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- Prior art keywords
- chlorine dioxide
- partition wall
- flue gas
- gas
- feedstock
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- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000004155 Chlorine dioxide Substances 0.000 title claims abstract description 55
- 235000019398 chlorine dioxide Nutrition 0.000 title claims abstract description 55
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003546 flue gas Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000002994 raw material Substances 0.000 title abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000010521 absorption reaction Methods 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 27
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 24
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 24
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 24
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 24
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 24
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 239000000292 calcium oxide Substances 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 14
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 14
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 14
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 44
- 238000005192 partition Methods 0.000 claims description 44
- 238000002156 mixing Methods 0.000 claims description 39
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 21
- 230000023556 desulfurization Effects 0.000 abstract description 21
- 230000003009 desulfurizing effect Effects 0.000 abstract description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002912 waste gas Substances 0.000 abstract description 4
- 239000003463 adsorbent Substances 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- QKIRHLCRDJURQV-UHFFFAOYSA-K calcium;sodium;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Na+].[Ca+2] QKIRHLCRDJURQV-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B11/00—Oxides or oxyacids of halogens; Salts thereof
- C01B11/02—Oxides of chlorine
- C01B11/022—Chlorine dioxide (ClO2)
- C01B11/023—Preparation from chlorites or chlorates
- C01B11/024—Preparation from chlorites or chlorates from chlorites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to the technical field of waste gas desulfurization, in particular to a method for desulfurizing flue gas SO (sulfur dioxide) 2 Method and system for preparing steady-state chlorine dioxide from raw materials and SO in flue gas 2 And then react with sodium chlorite, sodium pyrophosphate and chlorine gas fed into a tubular absorption reactor to generate liquid ClO 2 The liquid ClO 2 And (3) the chlorine dioxide solid powder product is generated after the chlorine dioxide solid powder product enters a reaction kettle and is adsorbed by calcium oxide and microcrystalline cellulose. The invention does not adopt strong acid, thus improving the safety of the reaction; calcium oxide is taken as a stabilizer of chlorine dioxide, microcrystalline cellulose is added as an adsorbent, and the mixture is directly reacted to generate solid powder of the chlorine dioxide, and the solid powder of the chlorine dioxide is dried to obtain a product; adopts a tube array type absorption reactor, and utilizes high-speed liquid flow to form negative pressure in the tube to absorb SO 2 And chlorine, and reacts in the main pipe to generate chlorine dioxide, and the absorption and conversion efficiency is higher than that of the traditional absorption tower.
Description
Technical Field
The invention relates to the technical field of waste gas desulfurization, in particular to a method for desulfurizing flue gas SO (sulfur dioxide) 2 A method and system for producing steady state chlorine dioxide for a feedstock.
Background
China is the largest SO in the world 2 National, annual SO emissions 2 The emission reduction is increased year by year. At present, coal-fired SO is commonly used at home and abroad 2 The control technology is mainly divided into pre-combustion desulfurization, in-combustion desulfurization and post-combustion flue gas desulfurization. Desulfurization before combustion is carried out by burning coalPreviously, sulfur content in raw coal was controlled by washing and the like. The desulfurization in combustion is mainly a circulating fluidized bed combustion desulfurization technology and a furnace calcium spraying and tail humidifying activation technology at present. Desulfurization efficiency of desulfurization technology before and during combustion is limited, and SO in China is along with 2 Increasingly stringent emission standards, flue gas desulfurization is becoming a control of coal-fired SO 2 The necessary route for discharge. The flue gas desulfurization technology capable of realizing recycling of desulfurization byproducts comprises a limestone-gypsum wet method, a double-alkali method, a magnesium oxide method, an ammonia method, a circulating fluidized bed semi-dry method, a sodium citrate absorption and analysis method, a regenerated organic amine absorption and analysis method, an active carbon adsorption method and the like.
The limestone-gypsum wet desulfurization has the advantages of mature technical process, higher desulfurization efficiency and the like, and becomes the most widely applied desulfurization technology at present. In the technology, the desulfurizing agent is limestone, which is a non-renewable desulfurizing agent, and the natural environment is seriously damaged by limestone exploitation. The desulfurization product is desulfurized gypsum (CaSO) 4 ·2H 2 O), often used as a building material, but desulfurized gypsum has a higher water content, poorer quality, lower value, high transportation cost, and transportation cost often exceeds the value of gypsum itself. At present, a large amount of desulfurization gypsum produced every year in China is discarded, so that pollution transfer is caused.
Due to SO in China 2 The emission is huge, and a large amount of desulfurization byproducts are produced while a large amount of desulfurizing agents are consumed in flue gas desulfurization, so that the problem of recycling the byproducts of the flue gas desulfurization technology is more concerned.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a method for preparing SO with flue gas 2 Method and system for preparing steady state chlorine dioxide from waste gas 2 And cheap chlorine is used as a raw material to prepare chlorine dioxide, strong acid is not adopted, and the safety of the reaction is improved.
In order to achieve the aim, the invention provides the technical proposal that the flue gas SO 2 Method for preparing steady-state chlorine dioxide from raw materials by using SO in flue gas 2 Reaction with sodium chlorite, sodium pyrophosphate and chlorine gas fed into tubular absorption reactorProduction of liquid ClO 2 The liquid ClO 2 And (3) the chlorine dioxide solid powder product is generated after the chlorine dioxide solid powder product enters a reaction kettle and is adsorbed by calcium oxide and microcrystalline cellulose.
Preferably, the concentration of the sodium chlorite is 0.2mol/L-0.3mol/L, and the concentration of the sodium pyrophosphate is 0.02mol/L-0.03mol/L of aqueous solution.
Preferably, the volume ratio of sodium chlorite to sodium pyrophosphate fed into the tubular absorption reactor is 1:1.
further, the tail gas after the reaction in the tubular absorption reactor is introduced into a reaction kettle.
In another aspect, the invention provides a method for treating SO with flue gas 2 The system for preparing steady-state chlorine dioxide for raw materials comprises a mixing tank, a sodium chlorite storage tank, a sodium pyrophosphate storage tank, a tubular absorption reactor and a reaction kettle; the sodium chlorite storage tank is connected with the mixing tank; the sodium pyrophosphate storage tank is connected with the mixing tank; the tubular absorption reactor is connected with the mixing tank and provided with a chlorine inlet and SO 2 The chlorine gas inlet is connected with a chlorine gas bottle, and the SO is provided with a chlorine dioxide liquid outlet and a tail gas outlet 2 The gas inlet is connected with an external flue gas pipeline; the reaction kettle is connected with the chlorine dioxide liquid outlet, and calcium oxide and microcrystalline cellulose are accommodated in the reaction kettle.
Further, the sodium chlorite storage tank is connected with the mixing tank through a first pipeline, and a first metering pump is arranged on the first pipeline.
Further, the sodium pyrophosphate storage tank is connected with the mixing tank through a second pipeline, and a second metering pump is arranged on the second pipeline.
Further, the mixing tank is connected with the tubular absorption reactor through a third pipeline, and a jet pump is arranged on the third pipeline.
Further, a gas distributor is arranged in the reaction kettle, and the tail gas outlet is connected to the gas distributor through a pipeline.
Further, the shell and tube absorption reactor includes many single tubes that are parallel to each other, the single tube includes the body is inside to be provided with first division wall and the second division wall, the inboard of first division wall separates out the convergent chamber, the inboard of second division wall separates out the divergent chamber, the tip of convergent chamber with the tip of divergent chamber sets up relatively, the outside of the inside first division wall of body is provided with the third division wall, the outside of the inside second division wall of body is provided with the fourth division wall, the third division wall and the fourth division wall separate out the mixing chamber with the space outside first division wall and the second division wall, mixing chamber UNICOM convergent chamber and divergent chamber, the body has been seted up liquid entry, liquid entry UNICOM extremely the convergent chamber has been seted up to the body, gas entry UNICOM extremely mixing chamber.
Further, the first partition wall and the second partition wall are both conical, and the third partition wall and the fourth partition wall are both annular.
The invention has the beneficial effects that: by SO in exhaust gas 2 And cheap chlorine is used as a raw material to prepare chlorine dioxide, strong acid is not adopted, and the safety of the reaction is improved; calcium oxide is taken as a stabilizer of chlorine dioxide, microcrystalline cellulose is added as an adsorbent, and the mixture is directly reacted to generate solid powder of the chlorine dioxide, and the solid powder of the chlorine dioxide is dried to obtain a product; adopts a tube array type absorption reactor, and utilizes high-speed liquid flow to form negative pressure in the tube to absorb SO 2 And chlorine, and reacts in the main pipe to generate chlorine dioxide, and the absorption and conversion efficiency is higher than that of the traditional absorption tower.
Drawings
FIG. 1 shows the flue gas SO according to an embodiment of the invention 2 A process flow diagram for preparing steady-state chlorine dioxide for a raw material;
FIG. 2 is a schematic view showing the structure of a single tube in a tubular absorption reactor according to an embodiment of the present invention;
in the figure: 100. a mixing tank is arranged on the upper surface of the mixing tank,
200. a sodium chlorite storage tank,
300. a storage tank for sodium pyrophosphate,
400. tubular absorption reactor 410, chlorine inlet, 420, SO 2 Gas inlet, 430, chlorine dioxide liquid outlet, 440, tail gas outlet, 450, single tube, 451, tube, 4511, liquid inlet, 4512, gas inlet, 452, first dividing wall, 453, second dividing wall, 454, converging chamber, 455, diverging chamber, 456, third dividing wall, 457, fourth dividing wall, 458, mixing chamber,
500. a reaction kettle, 510 and a gas distributor,
600. a chlorine cylinder is used for the chlorine cylinder,
700. the first conduit, 710, the first metering pump,
800. a second pipeline, 810, a second metering pump,
900. third pipe, 910, jet pump.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
One embodiment of the invention provides the flue gas SO 2 Method for preparing steady-state chlorine dioxide from raw materials by using SO in flue gas 2 And reacts with sodium chlorite, sodium pyrophosphate and chlorine gas fed into the tubular absorption reactor 400 to generate liquid ClO 2 . The reaction equation is as follows:
SO 2 +Cl 2 +2H 2 O→H 2 SO 4 +2HCl
5NaClO 2 +2H 2 SO 4 →4ClO 2 +2Na 2 SO 4 +NaCl+2H 2 O
5NaClO 2 +4HCl→4ClO 2 +5NaCl+2H 2 O
then enters a reaction kettle 500 to be adsorbed by calcium oxide and microcrystalline cellulose to generate a chlorine dioxide solid powder product.
The method for preparing steady-state chlorine dioxide uses SO in waste gas 2 And cheap chlorine is used as a raw material to prepare steady-state chlorine dioxide, strong acid is not needed, and the safety of the reaction is improved. Calcium oxide is taken as a stabilizer of chlorine dioxide, microcrystalline cellulose is added as an adsorbent, and the calcium oxide is directly reacted to generate solid powder of the chlorine dioxide, and the product is obtained after drying. By means of a tube array type absorption reactor 400, i.e. by means of a high-speed liquid flow, negative pressure is formed in the tube to absorb SO 2 And chlorine, and reacts in the main pipe to generate chlorine dioxide, and the absorption and conversion efficiency is higher than that of the traditional absorption tower.
Further, in one embodiment, the tail gas after the reaction in the shell-and-tube absorber 400 enters the reactor 500 through the gas distributor 510 in the reactor 500. Residual SO in tail gas 2 And sodium hydroxide calcium generated after chlorine gas is absorbed by calcium oxide in the reaction kettle 500, the reaction equation is as follows:
CaO+H 2 O→Ca(OH) 2 ；
Ca(OH) 2 +SO 2 →CaSO 3 +H 2 O；
Ca(OH) 2 +Cl 2 →CaCl 2 +H 2 O。
SO arranged, the tail gas in the reaction kettle 50 enters the reaction kettle through the gas distributor 510 to play a role in stirring, and residual SO in the tail gas 2 And chlorine can be absorbed by reacting with calcium oxide, so that no pollution gas is discharged.
Preferably, in one embodiment, sodium chlorite is used at a concentration of 0.2mol/L to 0.3mol/L and sodium pyrophosphate is used at a concentration of 0.02mol/L to 0.03mol/L in aqueous solution.
Preferably, in one embodiment, the volume ratio of sodium chlorite to sodium pyrophosphate fed to the tubular absorber reactor 400 is 1:1, a step of; further, SO 2 The volume ratio of the chlorine to the chlorine is 1:1. when the metering pump is specifically arranged, the metering pump can be used for feeding in an equal volume.
Preferably, the concentration of the calcium oxide is 20-40g/L, and the content of the microcrystalline cellulose is 10-20g/L.
One embodiment of the present invention provides a method ofBy flue gas SO 2 The system for preparing steady-state chlorine dioxide for raw materials comprises a mixing tank 100, a sodium chlorite storage tank 200, a sodium pyrophosphate storage tank 300, a tubular absorption reactor 400 and a reaction kettle 500, wherein sodium chlorite stored in the sodium chlorite storage tank 200 and sodium pyrophosphate stored in the sodium pyrophosphate storage tank 300 are sent into the mixing tank 100 for mixing and then are sent into the tubular absorption reactor 400; the sodium chlorite storage tank 200 is connected with the mixing tank 100; the sodium pyrophosphate storage tank 300 is connected with the mixing tank 100; the tubular absorption reactor 400 is connected with the mixing tank 100, and the tubular absorption reactor 400 is provided with a chlorine inlet 410 and SO 2 A gas inlet 420, a chlorine dioxide liquid outlet 430 and a tail gas outlet 440, wherein the chlorine gas inlet 410 is connected with a chlorine cylinder 600, SO 2 The gas inlet 420 is connected to an external flue gas duct (not shown in the drawings); the reaction kettle 500 is connected with a chlorine dioxide liquid outlet 430, and calcium oxide and microcrystalline cellulose are accommodated in the reaction kettle 500. Preferably, the reaction vessel 500 contains calcium oxide (concentration of 20-40 g/L) and microcrystalline cellulose (concentration of 10-20 g/L).
The specific process of the reaction is as follows: raw materials of sodium chlorite storage tank 200 and sodium pyrophosphate storage tank 300 are introduced into a mixing tank 100, the mixed liquid enters a tubular absorption reactor 400, meanwhile, chlorine in a chlorine cylinder 600 enters the tubular absorption reactor 400 from a chlorine inlet 410 so 2 From SO gas 2 The gas inlet 420 enters the shell and tube absorption reactor 400, liquid chlorine dioxide is generated after the reaction and enters the reaction kettle 500, and the chlorine dioxide reacts with calcium oxide and microcrystalline cellulose in the reaction kettle 500 to form a chlorine dioxide solid powder product.
In one embodiment, sodium chlorite storage tank 200 is connected to mixing tank 100 by a first conduit 700 with a first metering pump 710 disposed on first conduit 700.
In one embodiment, the sodium pyrophosphate storage tank 300 is connected to the mixing tank 100 by a second pipe 800, and a second metering pump 810 is provided on the second pipe 800.
It should be noted that, the first metering pump 710 is disposed on the first pipe 700, and the second metering pump 810 is disposed on the second pipe 800, so that the equal volume of the materials in the sodium chlorite storage tank 200 and the sodium pyrophosphate storage tank 300 can be monitored and controlled to be counted into the mixing tank 100, which is more beneficial to the reaction.
In one embodiment, the mixing tank 100 is connected to the shell-and-tube absorber 400 through a third pipe 900, and a jet pump 910 is disposed on the third pipe 900.
It should be noted that, the ejector pump 910 is disposed upstream of the tubular absorption reactor 400, which is more beneficial to mixing the reactants.
In one embodiment, a gas distributor 510 is provided inside the reaction vessel 500, and the tail gas outlet 440 is connected to the gas distributor 510 through a pipe. By the arrangement, the tail gas entering the reaction kettle 500 can be distributed more uniformly inside the reaction kettle 500, so that the reaction efficiency of the liquid chlorine dioxide, the calcium oxide and the microcrystalline cellulose is improved, and the yield of steady-state chlorine dioxide is improved. The reaction byproducts in the tubular absorption reactor 400 all enter the reaction kettle 500, and no residual liquid is discharged; in the reaction kettle 500, the tail gas enters the reaction kettle 500 through the gas distributor 510 to play a role in stirring, and residual SO in the tail gas 2 And chlorine can be absorbed by reacting with calcium oxide, so that no pollution gas is discharged.
In an embodiment, the shell-and-tube absorber 400 includes a plurality of single tubes 450 parallel to each other, the single tubes 450 include a tube body 451, a first partition wall 452 and a second partition wall 453 are disposed inside the tube body 451, a tapered chamber 454 is partitioned from the inner side of the first partition wall 452, a diverging chamber 455 is partitioned from the inner side of the second partition wall 453, a third partition wall 456 is disposed at the outer side of the first partition wall 452 inside the tube body 451, a fourth partition wall 457 is disposed at the outer side of the second partition wall 453 inside the tube body 451, the third partition wall 456 and the fourth partition wall 457 partition the space between the first partition wall 452 and the outer side of the second partition wall 453 into a mixing chamber 458, the tapered chamber 454 and the diverging chamber 455 are communicated with each other, a liquid inlet 4511 is formed in the tube body 451, a gas inlet 4512 is formed in the tube body 451, and the gas inlet 4512 is communicated with the mixing chamber 458.
The specific process of the reaction is as follows: high-velocity liquid flow containing sodium chlorite and sodium pyrophosphate entering through liquid inlet 4511 is taperedChamber 454 creates a negative pressure in mixing chamber 458, with the chlorine and SO entering through gas inlet 4512 2 The gas is drawn into mixing chamber 20 and reacts in diverging chamber 455 and tube 451 to form chlorine dioxide.
In one embodiment, the first partition wall 452 and the second partition wall 453 are conical, and the third partition wall 456 and the fourth partition wall 457 are annular.
The first partition wall 452 and the second partition wall 453 may have other shapes with gradually smaller cross-sectional radii than a cone, for example, a hemispherical shape, as long as the requirement of "gradually smaller diameter" is satisfied. The third partition 456 and the fourth partition 457 may be adaptively provided according to the specific shapes of the first partition 452 and the second partition 453.
In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present invention, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
It will be understood that when an element is referred to as being "fixed" or "disposed" on another element, it can be directly on the other element or intervening elements may also be present. When an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. The terms "vertical," "horizontal," "upper," "lower," "left," "right," and the like are used herein for illustrative purposes only and are not meant to be the only embodiment.
Claims (10)
1. By flue gas SO 2 A method for preparing steady state chlorine dioxide for a feedstock, characterized by: SO in flue gas 2 And then react with sodium chlorite, sodium pyrophosphate and chlorine gas fed into a tubular absorption reactor to generate liquid ClO 2 The liquid ClO 2 And (3) the chlorine dioxide solid powder product is generated after the chlorine dioxide solid powder product enters a reaction kettle and is adsorbed by calcium oxide and microcrystalline cellulose.
2. In flue gas SO according to claim 1 2 A method for preparing steady state chlorine dioxide for a feedstock, characterized by: the concentration of the sodium chlorite is 0.2mol/L-0.3mol/L, and the concentration of the sodium pyrophosphate is 0.02mol/L-0.03mol/L of aqueous solution.
3. Flue gas SO according to claim 2 2 A method for preparing steady state chlorine dioxide for a feedstock, characterized by: the volume ratio of sodium chlorite to sodium pyrophosphate fed into the tubular absorption reactor is 1:1.
4. in flue gas SO according to claim 1 2 A method for preparing steady state chlorine dioxide for a feedstock, characterized by: the method also comprises the step of introducing the tail gas after the reaction in the tubular absorption reactor into the reaction kettle.
5. By flue gas SO 2 A system for preparing steady state chlorine dioxide for a feedstock, characterized by: comprising
A mixing tank;
a sodium chlorite storage tank connected with the mixing tank;
a sodium pyrophosphate storage tank connected with the mixing tank;
the tubular absorption reactor is connected with the mixing tank and provided with a chlorine inlet and SO 2 The chlorine gas inlet is connected with a chlorine gas bottle, and the SO is provided with a chlorine dioxide liquid outlet and a tail gas outlet 2 The gas inlet is connected with an external flue gas pipeline;
and the reaction kettle is connected with the chlorine dioxide liquid outlet, and calcium oxide and microcrystalline cellulose are accommodated in the reaction kettle.
6. In flue gas SO according to claim 5 2 A system for preparing steady state chlorine dioxide for a feedstock, characterized by:
the sodium chlorite storage tank is connected with the mixing tank through a first pipeline, and a first metering pump is arranged on the first pipeline.
7. In flue gas SO according to claim 5 2 A system for preparing steady state chlorine dioxide for a feedstock, characterized by: the sodium pyrophosphate storage tank is connected with the mixing tank through a second pipeline, and a second metering pump is arranged on the second pipeline; the mixing tank is connected with the tubular absorption reactor through a third pipeline, and a jet pump is arranged on the third pipeline.
8. In flue gas SO according to claim 5 2 A system for preparing steady state chlorine dioxide for a feedstock, characterized by: the inside gas distributor that is provided with of reation kettle, the tail gas export is connected to through the pipeline gas distributor.
9. In flue gas SO according to claim 5 2 A system for preparing steady state chlorine dioxide for a feedstock, characterized by: the tube array type absorption reactor comprises a plurality of single tubes which are parallel to each other, wherein each single tube comprises a tube body, a first partition wall and a second partition wall are arranged in the tube body, a converging chamber is separated from the inner side of the first partition wall, a diverging chamber is separated from the inner side of the second partition wall, the small end of the converging chamber and the small end of the diverging chamber are oppositely arranged, a third partition wall is arranged on the outer side of the first partition wall in the tube body, a fourth partition wall is arranged on the outer side of the second partition wall in the tube body, a mixing chamber is separated from the space on the outer side of the first partition wall and the space on the outer side of the second partition wall by the third partition wall and the fourth partition wall, the mixing chamber is communicated with the converging chamber and the diverging chamber, a liquid inlet is formed in the tube body, the liquid inlet is communicated with the converging chamber, and a gas inlet is formed in the tube body, and the gas inlet is communicated with the mixing chamber.
10. Flue gas SO according to claim 9 2 A system for preparing steady state chlorine dioxide for a feedstock, characterized by: the first partition wall and the second partition wall are conical, and the third partition wall and the first partition wallThe four partition walls are all circular.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060022360A1 (en) * | 2004-07-29 | 2006-02-02 | Chenniah Nanjundiah | Chlorine dioxide solution generator with temperature control capability |
| CN101024492A (en) * | 2007-02-09 | 2007-08-29 | 中北大学 | High-purity chlorine dioxide gas generating method and apparatus |
| KR20090058832A (en) * | 2007-12-05 | 2009-06-10 | 한국식품연구원 | Manufacturing apparatus of chlorine dioxide and manufacturing method thereof |
| CN102674256A (en) * | 2012-05-11 | 2012-09-19 | 华南理工大学 | Method for preparing high-purity chlorine dioxide and sodium chlorite by ferrous sulfide method |
| EP2662328A1 (en) * | 2012-05-07 | 2013-11-13 | Erich Dr. Schmid | Method and device for producing chlorine dioxide |
| WO2013180760A2 (en) * | 2012-01-09 | 2013-12-05 | Robert Richardson | Removal of atmospheric pollutants from gas, related apparatus, processes and uses thereof |
| CN104512866A (en) * | 2013-09-30 | 2015-04-15 | 高砂热学工业株式会社 | Chlorine dioxide gas generation apparatus |
| CN105000535A (en) * | 2015-08-21 | 2015-10-28 | 大连交通大学 | Chlorine dioxide generator using three-component solid raw materials and preparation method of chlorine dioxide |
| CN105417497A (en) * | 2015-12-15 | 2016-03-23 | 刘学思 | Production device and technology for high-concentration steady chlorine dioxide solution |
| KR102170628B1 (en) * | 2020-07-13 | 2020-10-27 | 유한회사 네오클 | System and Method for removing Nitrogen oxides and Sulfur dioxide in flue gas using gaseous chlorine dioxide |
| CN112169573A (en) * | 2020-11-26 | 2021-01-05 | 苏州仕净环保科技股份有限公司 | Flue gas desulfurization and denitrification process |
| CN214456850U (en) * | 2021-03-04 | 2021-10-22 | 白银新众合化工有限公司 | High-purity sodium chlorite waste-discharge-free production system |
| CN113634100A (en) * | 2020-05-11 | 2021-11-12 | 上海梅山钢铁股份有限公司 | Method for carrying out oxidation denitration on sintering flue gas by using chlorine dioxide |
| CN114146209A (en) * | 2021-11-25 | 2022-03-08 | 上海交通大学 | Solid slow-release air purifying agent and preparation method thereof |
-
2023
- 2023-03-29 CN CN202310319768.4A patent/CN116462160B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060022360A1 (en) * | 2004-07-29 | 2006-02-02 | Chenniah Nanjundiah | Chlorine dioxide solution generator with temperature control capability |
| CN101024492A (en) * | 2007-02-09 | 2007-08-29 | 中北大学 | High-purity chlorine dioxide gas generating method and apparatus |
| KR20090058832A (en) * | 2007-12-05 | 2009-06-10 | 한국식품연구원 | Manufacturing apparatus of chlorine dioxide and manufacturing method thereof |
| WO2013180760A2 (en) * | 2012-01-09 | 2013-12-05 | Robert Richardson | Removal of atmospheric pollutants from gas, related apparatus, processes and uses thereof |
| EP2662328A1 (en) * | 2012-05-07 | 2013-11-13 | Erich Dr. Schmid | Method and device for producing chlorine dioxide |
| CN102674256A (en) * | 2012-05-11 | 2012-09-19 | 华南理工大学 | Method for preparing high-purity chlorine dioxide and sodium chlorite by ferrous sulfide method |
| CN104512866A (en) * | 2013-09-30 | 2015-04-15 | 高砂热学工业株式会社 | Chlorine dioxide gas generation apparatus |
| CN105000535A (en) * | 2015-08-21 | 2015-10-28 | 大连交通大学 | Chlorine dioxide generator using three-component solid raw materials and preparation method of chlorine dioxide |
| CN105417497A (en) * | 2015-12-15 | 2016-03-23 | 刘学思 | Production device and technology for high-concentration steady chlorine dioxide solution |
| CN113634100A (en) * | 2020-05-11 | 2021-11-12 | 上海梅山钢铁股份有限公司 | Method for carrying out oxidation denitration on sintering flue gas by using chlorine dioxide |
| KR102170628B1 (en) * | 2020-07-13 | 2020-10-27 | 유한회사 네오클 | System and Method for removing Nitrogen oxides and Sulfur dioxide in flue gas using gaseous chlorine dioxide |
| CN112169573A (en) * | 2020-11-26 | 2021-01-05 | 苏州仕净环保科技股份有限公司 | Flue gas desulfurization and denitrification process |
| CN214456850U (en) * | 2021-03-04 | 2021-10-22 | 白银新众合化工有限公司 | High-purity sodium chlorite waste-discharge-free production system |
| CN114146209A (en) * | 2021-11-25 | 2022-03-08 | 上海交通大学 | Solid slow-release air purifying agent and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| BYUN, Y ET AL.: "Formation of chlorinated species through reaction of SO2 with NaClO2 powder and their role in the oxidation of NO and Hg0", 《ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH》, 31 July 2014 (2014-07-31) * |
| PARK, HW AND PARK, DW: "Removal kinetics for gaseous NO and SO2 by an aqueous NaClO2 solution mist in a wet electrostatic precipitator", 《ENVIRONMENTAL TECHNOLOGY》, 31 December 2017 (2017-12-31) * |
| 刘伟: "新型碱液-超声波雾化式废气脱硫脱硝关键技术研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, 15 September 2020 (2020-09-15) * |
| 刘张义: "气体二氧化氯快速制备技术及其在消毒中的应用研究", 《中国消毒学杂志》, 15 June 2021 (2021-06-15) * |
| 李东;: "稳态二氧化氯溶液的制备及其在废气处理中的应用", 塑料工业, no. 05, 20 May 2012 (2012-05-20) * |
| 田颖等: "二氧化氯的稳定和活化方法研究", 《环境保护科学》, 20 June 2002 (2002-06-20) * |
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