CN102626660A - Becky regular catalytic filter for sea water flue gas desulfurization and preparation method thereof - Google Patents
Becky regular catalytic filter for sea water flue gas desulfurization and preparation method thereof Download PDFInfo
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- CN102626660A CN102626660A CN2012100861209A CN201210086120A CN102626660A CN 102626660 A CN102626660 A CN 102626660A CN 2012100861209 A CN2012100861209 A CN 2012100861209A CN 201210086120 A CN201210086120 A CN 201210086120A CN 102626660 A CN102626660 A CN 102626660A
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- shellfish
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- flue gas
- mixture
- gas desulfurization
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- 239000013535 sea water Substances 0.000 title claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 29
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 26
- 239000003546 flue gas Substances 0.000 title claims abstract description 26
- 230000023556 desulfurization Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 235000015170 shellfish Nutrition 0.000 claims description 29
- 238000011049 filling Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 16
- 238000012856 packing Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 235000013379 molasses Nutrition 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 238000003483 aging Methods 0.000 claims description 4
- 239000004568 cement Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000009938 salting Methods 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920002261 Corn starch Polymers 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 241000721619 Najas Species 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 239000000571 coke Substances 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229920001206 natural gum Polymers 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 239000011505 plaster Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 229940072033 potash Drugs 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000003916 acid precipitation Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000003009 desulfurizing effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 241000276489 Merlangius merlangus Species 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses a Becky regular catalytic filter for sea water flue gas desulfurization and a preparation method thereof. The method is characterized by comprising the following steps of crushing and grinding Becky material to be in 20-30 meshes; mixing binder, pore-forming agent and lubricating agent with water according to the mass parts of (40-80):(15-40):(0.3-10):(0.5), and forming waved shapes on a forming machine; maintaining for 1-4 weeks under steam with temperature of 60-150 DEG C, so as to obtain regular filler with certain strength; soaking for 1-24h by adding the regular filler (according to a proportion of 8-10 ml/g) into active component solution with metal ionic concentration of 0.7 mol/L-1.5 mol/L by 1-8 times, adding the regular filler (according to a proportion of 7-10 ml/g) into saturated precipitator solution, aging for 3-18h, filtering, washing, drying, carrying out temperature rising in an oven, so as to obtain the Becky regular catalytic filter for the sea water flue gas desulfurization, wherein the temperature rising speed is 10 DEG C/min, the calcination temperature is below 250-650 DEG C, the air flow can be kept during the temperature rising and constant temperature processes, and the calcination time under constant temperature is 2-4h.
Description
Technical field
The present invention relates to a kind of catalytic filler that is used for the use of flue gas desulfurization with seawater technology and preparation method thereof, particularly a kind of shell base regulation catalytic filling that utilizes discarded natural shellfish preparation and preparation method thereof.
Background technology
China is SO
2Discharging big country, SO
2Annual emissions surpasses 2.0 * 10
7T occupies first of the world, by SO
2The acid rain area that pollution causes has accounted for 30% of area.Coal burning is China atmosphere SO
2Main source; Its discharge capacity accounts for more than 85% of total release; Cause China's acid rain area constantly to enlarge, existing to expand to the most of areas in southwest, Central China, south China and East China from southwestern some areas, China also becomes the another world acid rain district after West Europe, North America.SO
2Not only destroy the environment and the ecosystem with acid rain, the more important thing is the serious harm people ' s health, become restriction China's economic development and socially harmonious key factor.The up-to-date environmental data of announcing in 2008 according to State Environmental Protection Administration shows, the SO in the whole nation
2Discharge capacity surpasses 2,000 ten thousand tons for years, derives from industrial discharge more than 80%, and therefore the work of control and improvement sulfur dioxide can not pause.
Flue gas desulfurization (FGD) is to control SO at present in the world
2Main and the effective desulfurization method that pollute, control acid rain endangers.Wherein the sea water desulfuration technology belongs to a kind of in the wet desulphurization technology, and this technique functions starts from the seventies in 20th century, and applies in Coastal Power Station such as Europe, America, Asia very soon.The large-scale unit flue gas desulfurization with seawater of thermal power plant technology is mature on the whole abroad at present, and its sea water desulfuration technology can be divided into two types: the one, do not add any chemical substance, with full sea water as SO
2The technology of absorption liquid, this technology is representative with the Flakt-Hydro technology of Norway ABB AB exploitation, is widely used; Another is in seawater, to add a certain amount of lime or limy material, to regulate the basicity of absorption liquid, strengthens assimilation effect, and this technology is representative with the white clay sulfur removal technology of U.S. Bechte company and professor Wang Qingzhang of Chinese Marine University exploitation.At present adopt the former more, promptly do not add the method for any chemical substance.
At present existing seawater desulfurizing process is unsatisfactory greater than 2% coal desulfurization effect to sulfur content, if the hypomere filling can oxidation SO on the absorption tower
2Catalyst, at Absorption by Sea Water SO
2The time carry out SO
2Catalytic oxidation, then can significantly improve the desulfuration efficiency on absorption tower.Present seawater SO
2The catalyst of oxidation mainly is divided into two big types: metal oxide and active carbon.Although active carbon still keeps higher catalytic oxidation activity under acid condition; But since the rate determining step of catalytic oxidation process be suddenly in the seawater dissolved oxygen in the absorption of active sites; Whole sweetening process takes place in heterogeneous system, heterogeneous catalytic oxidation SO under this condition
2Reaction possibly take place hardly.And metal oxide can well with SO
2In conjunction with, can rapidly and efficiently remove the SO in the flue gas
2And advantages such as the load type metal oxidation catalyst can use because of it repeatedly, and post processing is simple have been widely applied in a lot of technical process.Be vanadium pentoxide catalyst, copper oxide catalyst, manganese oxide catalyst, ferric oxide catalyst by the metal oxide catalyst of broad research and application at present.The selection of carrier has crucial effects for catalyst activity and selectivity, life-span, mechanical strength, cost, and is because of shellfish sill wide material sources, cheap; Belong to twice laid; Characteristic picture pottery, seawater corrosion resistance, iterative regenerable recycles; Non-secondary pollution can progressively replace advantages such as pottery or regular plastic filler and in flue gas desulfurization with seawater technology, have broad application prospects.
Summary of the invention
The purpose of this invention is to provide a kind of the utilization and discard the regulation catalytic filling that the shellfish preparation is used for flue gas desulfurization with seawater.
Another object of the present invention provides the preparation method of above-mentioned shellfish base regulation catalytic filling.
Technical scheme of the present invention is following: a kind of shellfish base regulation catalytic filling that is used for flue gas desulfurization with seawater is characterized in that it may further comprise the steps: 1. with shellfish sill crushing grinding to the 20-300 order; 2. the shellfish sill that 1. step is obtained and binding agent, pore creating material and lubricant are according to (40-80): (15-40): (0.3-10): mass fraction (0.5-2) adds water and mixes, and on make-up machine, processes the ripple type shape; 3. the shaped article that 2. step is obtained is in 60-150 ℃ of following steam maintenance 1-4 week, the structured packing that obtains having certain intensity; 4. the structured packing that 3. step is obtained joins in the active component salting liquid that concentration of metal ions is 0.7mol/L-1.5mol/L according to the ratio of every gram 8-10ml floods 1-24h; The dipping number of times is 1 ~ 8 time, and the ratio according to every gram structured packing 7-10ml adds saturated precipitant solution again, ageing 3-18h; Filtration, washing, drying; Be placed on the interior heating rate of baking oven and heat up, under 250 ~ 650 ℃ of sintering temperatures, keep air to flow in intensification and the thermostatic process with 10 ℃/min; The constant temperature calcining time is 2-4h, promptly makes the support type shellfish base regulation catalytic filling that is used for flue gas desulfurization with seawater.
Described shellfish sill is one or more the mixture in naiad shell, the conch shellfish shell.
Described binding agent is waterglass+CaCl
2, one or more mixture and/or pitch, resin, polyvinyl alcohol, methylcellulose, desulfurated plaster, cement, paraffin, one or more the mixture in the clay in the aluminium colloidal sol, Ludox, molasses, natural gum, dried starch, bentonite, animal glue, gelatinized corn starch.
Described pore creating material is one or more the mixture in carbon black, active carbon, activated coke, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, polyethylene glycol, molasses, the POLYPROPYLENE GLYCOL.
Described lubricant is one or more the mixture in water, glycerine, lubricating oil, soluble oil and water, silicones, polyacrylamide and/or talcum powder, graphite, dolomol or other stearate, molybdenum bisuphide, dried starch, sesbania powder, the paraffin.
The mixture of one or more in the soluble-salt solution that described active component salting liquid is manganese, iron is like sulfate of ferrous iron and bivalent manganese etc.
Said precipitating reagent is one or more the mixture in ammonium carbonate, sodium carbonate, the potash.
The present invention utilizes the shellfish base regulation catalytic filling that is used for flue gas desulfurization with seawater of marine natural shellfish preparation to have the following advantages: seawater desulfurizing process uses pottery or regular plastic filler; The type filler uses the shell sill; The source is wide; Cheap, iterative regenerable recycles, non-secondary pollution; Shellfish sill anti-seawater corrosion has longer life; Profile is designed to the ripple type shape, thus greatly flux pass through seawater, be beneficial to the gas-liquid exchange, improve desulfuration efficiency; Select iron and manganese oxides as active component,, can not cause ocean heavy metal pollution because its trace element and number of dropouts that is in the seawater is small, and with flue gas in SO
2Stronger binding ability is arranged, can remove SO in the flue gas fast
2And the simple iterative regenerable utilization of post processing is to SO in the flue gas
2Has higher removal efficiency.
The specific embodiment
Specify the present invention through specific embodiment below.
Embodiment 1:
Be after the 40-100 order oyster shell whiting, cement (binding agent), molasses (pore creating material), talcum powder (lubricant) of 45g adds water and mix by the mass ratio of 60:24.5:4.9:0.5, to put into mould with gross mass in 28Mpa pressurization 30min moulding down; Under 120 ℃ water vapor conditions, carry out 3 weeks of maintenance, make structured packing with certain intensity; It is immersed 400ml concentration is the MnSO of 0.9mol/L
4In the solution, 60 ℃ of stirring conditions flooded 8 hours down, and the dipping number of times is 1 time, dripped saturated ammonium sulfate solution 360ml altogether again; From precipitation solution, take out and, spend deionised water 40 ℃ of ageings 6 hours, in 120 ℃ of dryings 4 hours, 350 ℃ of roastings 3 hours and make load 5.8% (wt%) MnO
2Shellfish base regulation catalytic filling.The catalyst desulfurizing active appraisal experiment is following: above-mentioned structured packing is packed in the packed tower, carry out the flue gas desulfurization with seawater experiment; Go into 30 ℃ of tower ocean temperatures, seawater flow is respectively 20,40,60,80L/h, and corresponding respectively liquid-gas ratio is 4.0,6.0,7.0,8.0L/Nm
3Going into tower simulated flue gas flow is 10Nm
3/ h, flue gas SO
2Concentration is 2100mg/m
3, wherein simulated flue gas is by air and high concentration SO
2Gas mixes.Load MnO
2Catalytic filler SO
2Remove reaction effect such as table 1.
Table 1 load MnO
2Front and back shellfish base regulation catalytic filling SO
2Removal efficiency
Can find out load MnO
2Shellfish base regulation catalytic filling ratio is load MnO not
2Shellfish base structured packing desulfurization degree exceeds 4-10%, significant desulfurization effect.
Embodiment 2:
Be after 100-200 order oyster shell whiting cement (binding agent), graphite (lubricant) and the molasses (pore creating material) of 45g add water and mix by the mass ratio of 70:22.5:0.5:2, to put into mould with gross mass in 25Mpa pressurization 30min moulding down; Under 150 ℃ water vapor conditions, carry out 4 weeks of maintenance, make structured packing with certain intensity; It is immersed 200ml concentration is the MnSO of 0.9mol/L
4With 200ml concentration be the FeSO of 0.9mol/L
4In the mixed solution, 60 ℃ of stirring conditions flooded 8 hours down, and the dipping number of times is 1 time, dripped saturated ammonium sulfate solution 360ml altogether again; From precipitation solution, take out and, spend deionised water 40 ℃ of ageings 6 hours, in 120 ℃ of dryings 4 hours, 350 ℃ of roastings 3 hours and make load 2.9%MnO
2, 5.3%Fe
2O
3Shellfish base regulation catalytic filling.The catalyst desulfurizing active appraisal experiment is following: the structured packing that load is finished is packed in the packed tower, is to carry out the flue gas desulfurization with seawater experiment under 15,30,55 ℃ in reaction temperature; Go into tower simulated flue gas flow 10Nm
3/ h, going into tower flue gas concentration is 2100mg/m
3, wherein simulated flue gas is by air and high concentration SO
2Gas mixes; Go into that the tower seawater flow is respectively 40,60,80,100L/h, corresponding respectively liquid-gas ratio is 4.0,6.0,7.0,8.0L/Nm
3Load MnO
2, Fe
2O
3Regulation catalytic filling removes SO
2Reaction effect such as table 2.
Load MnO under table 2 different temperatures
2, Fe
2O
3Front and back shellfish base regulation catalytic filling SO
2Removal efficiency
Can find out, will exceed 5-25%, significant desulfurization effect than the base of the shellfish before load regulation catalytic filling desulfurization degree after the load.
Claims (7)
1. the preparation method of a shellfish base regulation catalytic filling that is used for flue gas desulfurization with seawater is characterized in that it may further comprise the steps: 1. with shellfish sill crushing grinding to the 20-300 order; 2. the shellfish sill that 1. step is obtained and binding agent, pore creating material and lubricant are according to (40-80): (15-40): (0.3-10): mass fraction (0.5-2) adds water and mixes, and on make-up machine, processes the ripple type shape; 3. the shaped article that 2. step is obtained is in 60-150 ℃ of following steam maintenance 1-4 week, the structured packing that obtains having certain intensity; 4. the structured packing that 3. step is obtained joins in the active component salting liquid that concentration of metal ions is 0.7mol/L-1.5mol/L according to the ratio of every gram 8-10ml floods 1-24h; The dipping number of times is 1 ~ 8 time, and the ratio according to every gram structured packing 7-10ml adds saturated precipitant solution again, ageing 3-18h; Filtration, washing, drying; Be placed on the interior heating rate of baking oven and heat up, under 250 ~ 650 ℃ of sintering temperatures, keep air to flow in intensification and the thermostatic process with 10 ℃/min; The constant temperature calcining time is 2-4h, promptly makes the support type shellfish base regulation catalytic filling that is used for flue gas desulfurization with seawater.
2. the preparation method of shellfish according to claim 1 base regulation catalytic filling is characterized in that described shellfish sill is one or more the mixture in naiad shell, the conch shellfish shell.
3. according to the preparation method of the base of the shellfish described in the claim 1 regulation catalytic filling, it is characterized in that described binding agent is waterglass+CaCl
2, one or more mixture and/or pitch, resin, polyvinyl alcohol, methylcellulose, desulfurated plaster, cement, paraffin, one or more the mixture in the clay in the aluminium colloidal sol, Ludox, molasses, natural gum, dried starch, bentonite, animal glue, gelatinized corn starch.
4. the preparation method of shellfish according to claim 1 base regulation catalytic filling is characterized in that described pore creating material is one or more the mixture in carbon black, active carbon, activated coke, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide, polyethylene glycol, molasses, the POLYPROPYLENE GLYCOL.
5. the preparation method of shellfish according to claim 1 base regulation catalytic filling is characterized in that described lubricant is one or more the mixture in water, glycerine, lubricating oil, soluble oil and water, silicones, polyacrylamide and/or talcum powder, graphite, dolomol or other stearate, molybdenum bisuphide, dried starch, sesbania powder, the paraffin.
6. the preparation method of shellfish according to claim 1 base regulation catalytic filling is characterized in that one or more the mixture in the soluble-salt solution that described solubility active component salting liquid is manganese, iron.
7. the preparation method of shellfish according to claim 1 base regulation catalytic filling is characterized in that said precipitating reagent is one or more the mixture in ammonium carbonate, sodium carbonate, the potash.
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Cited By (6)
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| CN103191638A (en) * | 2013-04-16 | 2013-07-10 | 浙江大学 | Novel desulfurizer packing material for seawater desulfurization and preparation method thereof |
| CN103341305A (en) * | 2013-06-26 | 2013-10-09 | 哈尔滨工程大学 | Preparation method of packing used for improving efficiency of ship waste gas absorption tower |
| CN104209084A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Claus tail gas SO2Adsorbent, preparation and application thereof |
| CN112516780A (en) * | 2020-10-27 | 2021-03-19 | 蒲城驭腾新材料科技有限公司 | Calcium-based desulfurizer and preparation method thereof |
| CN113101978A (en) * | 2021-04-12 | 2021-07-13 | 上海三融环保工程有限公司 | Desulfurization catalyst applied to cement plant and preparation method thereof |
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| CN101693184A (en) * | 2009-10-25 | 2010-04-14 | 中国海洋大学 | Method for preparing ceramic regulation catalytic filling for sea water desulfuration |
| CN102302922A (en) * | 2011-07-18 | 2012-01-04 | 中国海洋大学 | Formed shellfish-based regular photocatalytic adsorbent and preparation method thereof |
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| CN101693184A (en) * | 2009-10-25 | 2010-04-14 | 中国海洋大学 | Method for preparing ceramic regulation catalytic filling for sea water desulfuration |
| CN102302922A (en) * | 2011-07-18 | 2012-01-04 | 中国海洋大学 | Formed shellfish-based regular photocatalytic adsorbent and preparation method thereof |
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| CN103191638A (en) * | 2013-04-16 | 2013-07-10 | 浙江大学 | Novel desulfurizer packing material for seawater desulfurization and preparation method thereof |
| CN103191638B (en) * | 2013-04-16 | 2016-01-06 | 浙江大学 | A kind of desulfurizing tower filler for sea water desulfuration and preparation method |
| CN104209084A (en) * | 2013-06-05 | 2014-12-17 | 中国石油天然气股份有限公司 | Claus tail gas SO2Adsorbent, preparation and application thereof |
| CN103341305A (en) * | 2013-06-26 | 2013-10-09 | 哈尔滨工程大学 | Preparation method of packing used for improving efficiency of ship waste gas absorption tower |
| CN112516780A (en) * | 2020-10-27 | 2021-03-19 | 蒲城驭腾新材料科技有限公司 | Calcium-based desulfurizer and preparation method thereof |
| CN113101978A (en) * | 2021-04-12 | 2021-07-13 | 上海三融环保工程有限公司 | Desulfurization catalyst applied to cement plant and preparation method thereof |
| CN113101978B (en) * | 2021-04-12 | 2023-02-17 | 上海三融环保工程有限公司 | Desulfurization catalyst applied to cement plant and preparation method thereof |
| CN113198430A (en) * | 2021-05-15 | 2021-08-03 | 兰州城市学院 | Preparation method of composite nano material |
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Application publication date: 20120808 |