EP3325581A1 - Ecological solid fuel additive, reducing soot formation - Google Patents
Ecological solid fuel additive, reducing soot formationInfo
- Publication number
- EP3325581A1 EP3325581A1 EP15787013.0A EP15787013A EP3325581A1 EP 3325581 A1 EP3325581 A1 EP 3325581A1 EP 15787013 A EP15787013 A EP 15787013A EP 3325581 A1 EP3325581 A1 EP 3325581A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon black
- fuel additive
- additive
- fuel
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000654 additive Substances 0.000 title claims abstract description 67
- 230000000996 additive effect Effects 0.000 title claims abstract description 64
- 239000004449 solid propellant Substances 0.000 title claims abstract description 16
- 239000004071 soot Substances 0.000 title description 21
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 239000006229 carbon black Substances 0.000 claims abstract description 187
- 239000002816 fuel additive Substances 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 29
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000010333 potassium nitrate Nutrition 0.000 claims abstract description 11
- 239000004323 potassium nitrate Substances 0.000 claims abstract description 11
- 229940045872 sodium percarbonate Drugs 0.000 claims abstract description 11
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims abstract description 10
- 150000002823 nitrates Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000004927 clay Substances 0.000 claims abstract description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims abstract description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002829 reductive effect Effects 0.000 claims abstract description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims abstract description 4
- 239000004317 sodium nitrate Substances 0.000 claims abstract description 4
- 231100000167 toxic agent Toxicity 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 abstract 1
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract 1
- 235000019241 carbon black Nutrition 0.000 description 183
- 241000196324 Embryophyta Species 0.000 description 76
- 238000002485 combustion reaction Methods 0.000 description 31
- 230000000694 effects Effects 0.000 description 28
- 239000000446 fuel Substances 0.000 description 27
- 241000872198 Serjania polyphylla Species 0.000 description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 235000015097 nutrients Nutrition 0.000 description 20
- 239000003245 coal Substances 0.000 description 18
- 239000000049 pigment Substances 0.000 description 13
- 230000003247 decreasing effect Effects 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 230000012010 growth Effects 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 10
- 239000011780 sodium chloride Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 102000001708 Protein Isoforms Human genes 0.000 description 8
- 108010029485 Protein Isoforms Proteins 0.000 description 8
- 102000019197 Superoxide Dismutase Human genes 0.000 description 8
- 108010012715 Superoxide dismutase Proteins 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 235000014469 Bacillus subtilis Nutrition 0.000 description 5
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000284 extract Substances 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000000243 photosynthetic effect Effects 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 241000219195 Arabidopsis thaliana Species 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 101710144724 Superoxide dismutase [Fe] Proteins 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 238000006065 biodegradation reaction Methods 0.000 description 4
- 150000001721 carbon Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000001962 electrophoresis Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 230000036542 oxidative stress Effects 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 244000063299 Bacillus subtilis Species 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 101710119418 Superoxide dismutase [Mn] Proteins 0.000 description 3
- 101710202572 Superoxide dismutase [Mn], mitochondrial Proteins 0.000 description 3
- 102100032891 Superoxide dismutase [Mn], mitochondrial Human genes 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000021466 carotenoid Nutrition 0.000 description 3
- 150000001747 carotenoids Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- -1 ferrous metals Chemical class 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 231100001231 less toxic Toxicity 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008635 plant growth Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000007226 seed germination Effects 0.000 description 3
- 244000000000 soil microbiome Species 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 2
- 210000003763 chloroplast Anatomy 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000035784 germination Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000001744 histochemical effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000013178 mathematical model Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 210000002824 peroxisome Anatomy 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 102000010750 Metalloproteins Human genes 0.000 description 1
- 108010063312 Metalloproteins Proteins 0.000 description 1
- 101100270435 Mus musculus Arhgef12 gene Proteins 0.000 description 1
- 231100000674 Phytotoxicity Toxicity 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000009141 biological interaction Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- 229930002868 chlorophyll a Natural products 0.000 description 1
- NSMUHPMZFPKNMZ-VBYMZDBQSA-M chlorophyll b Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C=O)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 NSMUHPMZFPKNMZ-VBYMZDBQSA-M 0.000 description 1
- 229930002869 chlorophyll b Natural products 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052963 cobaltite Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 210000000172 cytosol Anatomy 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003255 drug test Methods 0.000 description 1
- 238000000469 dry deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003988 headspace gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 244000005706 microflora Species 0.000 description 1
- 210000003470 mitochondria Anatomy 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 231100000255 pathogenic effect Toxicity 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012113 quantitative test Methods 0.000 description 1
- 239000010499 rapseed oil Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000007447 staining method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003442 weekly effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
- C10L9/12—Oxidation means, e.g. oxygen-generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/0204—Metals or alloys
- C10L2200/0209—Group I metals: Li, Na, K, Rb, Cs, Fr, Cu, Ag, Au
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/0204—Metals or alloys
- C10L2200/024—Group VIII metals: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/0272—Silicon containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2200/00—Components of fuel compositions
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/029—Salts, such as carbonates, oxides, hydroxides, percompounds, e.g. peroxides, perborates, nitrates, nitrites, sulfates, and silicates
Definitions
- the subject-matter of the invention is the ecological solid fuel additive, reducing soot formation.
- the fuel additive for soot combustion applied in operations of hard coal, lignite, fine coal, coke, anthracite, peat, pellets, coal briquettes and wood-burning furnaces as well as low, medium and high efficiency furnaces and boilers.
- the effective fuel additive allowing for reduction by deposit volume at the exchanger by 45- 55% is known from the Chinese patent CN 1010483.
- the fuel additive is a mixture of potassium nitrate (60-80%), ammonium nitrate, triiron tetroxide (0.1-1.0%), charcoal, borax, trisodium phosphate as chelating agent, magnesium, aluminum, sodium chloride and powdered sulphur.
- the additive is used in household and industrial installations and industrial coal-burning boilers.
- the additive modifies chemical and physical soot properties improving at the same time heating efficiency of the heat exchanger.
- the fuel additive is decomposable in 485°C, forming a coating on the heat exchanger surface and protecting it against corrosion.
- Coal additive to coal of low calorific value known from the Chinese CN 103305313 patent description contains 20-100% of active substance.
- Mixture of active substances contains 30- 80% in weight of calcium cobaltite (Ca 3 Co 4 0 9 ), 0-30% in weight of triiron tetroxide (Fe 3 0 4 ) and cerium dioxide (Ce0 2 ) and potassium oxide of several percents in weight.
- the fuel additive revealed in this invention decreases the fuel ignition temperature by 3-15°C, enhancing the combustion effectiveness and making coal combustion with fuel additive less polluting to the air comparing to fuel combustion without the fuel additive.
- soot combustion catalysts containing copper sulphate, sodium chloride and ammonium chloride are known from PL 207482 and PL 165406 patent description. Despite its advantages in combustion of lesser quantities of coal and lower risk of carbon deposities ignition in the flue pipes, this is not environmentally safe operation.
- the solid biomass additive containing among others the carboxylic acid salts and one or more metals from among the alkaline earth, lanthanide and ferrous metals; fatty acid esters and fatty acids or acidic resins, is known from the EP 0 725 128 B l patent.
- the fatty acid esters are, advantageously, methyl esters, in particulars of rape oil esters.
- the described additive enhances mechanical properties of biomass in the course of processing and reduces production of toxic fumes.
- the disadvantage of the described solution is no opportunity to apply the additive to any other fuels than pulverized one.
- Known fuel additives may be harmful to the environment (copper and chlorine compounds), cause excessive corrosion of boiler and flue pipes (chloride and sulphur compounds, fatty acid oxy-degradation products) and have pathogenic effect (cerium compounds).
- the subject-matter of the invention is the ecological solid fuel additive, composed of triiron tetroxide, nitrates, most frequently potassium nitrate(V) containing 30-60% in weight of triiron tetroxide (Fe 3 0 4 ), 10-30% in weight of potassium nitrate(V) (KN0 3 ), sodium nitrate(V) (NaN0 3 ), ammonium nitrate(V) (NH 4 N0 3 ), or mixture of the abovementioned nitrates(V), 5-30% in weight of sodium percarbonate (Na 2 C0 3 - 1,5H 2 0 2 ) and 10% in weight of anti-caking agent.
- the anti-caking agent is powdered burnt clay.
- Fe 3 0 4 used for fuel additive production is free from FeS0 4.
- soot production and toxic compounds present in soot is limited.
- Ecological solid fuel additive reducing soot production presented in the invention is a proposal for environment-friendly solid fuel combustion, preventing environmental contamination with soot accompanying pollutants such as: polyaromatic hydrocarbons (PAH), persistent organic radicals and heavy metals, whereas reduction of carbon black production prevents additionally the excessive fuel consumption (carbon black decreases the heating efficiency of a boiler) and increases combustion effectiveness.
- PHA polyaromatic hydrocarbons
- carbon black decreases the heating efficiency of a boiler
- Solid fuel additive according to the invention is characterized by that it contains 30-60% in weight of triiron tetroxide (Fe 3 0 4 ), 10-30% in weight of potassium nitrate(V) (KN0 3 ), sodium nitrate(V) (NaN0 3 ), ammonium nitrate(V) (NH 4 N0 3 ), or mixture of the abovementioned nitrates(V), 5-30% in weight of sodium percarbonate (Na 2 C0 3 - 1,5H 2 0 2 ) and 10% in weight of anti-caking agent e.g. powdered burnt clay.
- Triiron tetroxide Fe 3 0 4
- KN0 3 potassium nitrate(V)
- NaN0 3 sodium nitrate(V)
- NH 4 N0 3 ammonium nitrate(V)
- anti-caking agent e.g. powdered burnt clay.
- FeS0 4 may act as the raw material for Fe 3 0 4 production, which explains its presence). FeS0 4 presence in small quantities does not change the activity of fuel additive towards reducing the carbon black production, however carbon black obtained in presence of even small quantities of FeS0 4 is significantly less biodegradable (negative environmental impact).
- the additive according to the invention introduced to the combustion chamber with fuel or at the surface of the combusted fuel, is subject to partial thermal decomposition and releases the larg volume of gaseous products.
- Fuel additive components are activated in the temperature range of 80-650°C.
- Gaseous products of nitrates and sodium percarbonate decomposition reaction transport part of Fe 3 0 4 quantity onto the carbonaceous deposite surface covering the heat exchanger.
- Fe 3 0 4 particles in contact with heated fuel reach high temperature and then are transported on the carbonaceous deposite surface along with flue gas, where using its energy and catalytic oxidation properties catalyze the reaction of complete and total fuel combustion for hours.
- Decomposition of sodium percarbonate produces the peroxide and hydroxyl radicals, which, by means of chain reactions, are able to initiate the carbon black oxidation reaction.
- the chemical composition of the produced carbon black changes advantageously, in effect of which it contains less harmful substances. Modification of the composition in result of application of the ecological fuel additive facilitates biodegradation of substances contained in the carbon black, including cancerogenic polyaromatic hydrocarbons (PAH).
- PAH cancerogenic polyaromatic hydrocarbons
- the additive according to the invention should be used in quantity of 0.5-2 kg per 1000 kg of fuel, advantageously 1.2 kg per 1000 kg of fuel in the case of application of additive in mixture with fuel.
- Chemical composition of the additive is decisive for its value, however its dose i.e. weight proportion of the additive to fuel unit (1000 kg) is almost of equal importance.
- the sufficient quantity is 50 g of additive in weekly intervals. In the cases of tendency of the heat exchanger to intensive covering with deposite resulting from quality of combusted fuel or the structure of heating installation, it is necessary to increase the fuel additive dose or its more frequent application.
- the additive and produced carbon black is more environment- friendly. Combustion is more complete and produces less waste and smaller quantities of carbon black, which is additionally less toxic. There is also more energy produced.
- Solid fuel additive (coal, briquettes, etc.) according to the invention is a better ecological product than the additives in the composition, containing also: copper, chlorine, sulphur or fatty acids.
- the most significant pro-ecological effect of the fuel additive according to the invention is reduced carbon black production i.e. cancerogenic substance causing a greenhouse effect, carrier of polyaromatic hydrocarbons, stable organic radicals and heavy metals. Carbon black is also a pathogenic agent (circulatory and respiratory system diseases).
- Carbon black is a chemical and physical pollutant of air, water and soils, therefore its reduction constitutes a significant component of air protection programmes as well as the low emission reduction programmes (LERP).
- LEP low emission reduction programmes
- soot is a powerful absorbent of sunlight and contributes to climate warming and melting of glaciers covered with so called dry deposition (particulates) causing the greenhouse effect.
- Ecological effect of the additive according to the invention results also in lowering the combustion temperature and quantity of produced combustion gases, whereas the limited amount of produced soot is both less toxic and its components are biodegradable, and demonstrates the properties stimulating plant growth, including biomass increase.
- Figure 1 presents comparison of the content of the total of 4 components of soot sample determined using the HS-GC-MS method in the soot biodegradtion studies of two carbon black types
- Figure 2 presents the impact of carbon black (5% v/v) on the rate of occurrence of visible cotyledons of A. thaliana.
- NM carbon black - carbon black without fuel additive B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
- Figure 3 presents the impact of carbon black (5% v/v) on the rate of occurrence of the first leaf pair of A. thaliana. NM carbon black - carbon black without fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
- Figure 4 presents the impact of the studied types of carbon black (5% v/v) on mass increase of A. thaliana upon 2 and 4 weeks of cultivation.
- NM carbon black - carbon black without fuel additive B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A soot - carbon black with fuel additive according to the invention;
- Figure 5 presents the impact of the tested soot types (5% v/v) on pigment content in A. thaliana upon 4 weeks of cultivation.
- NM carbon black - carbon black without fuel additive B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
- Figure 6 presents the graph of A. thaliana superoxide dismutases (SOD) activity upon native electrophoresis and histochemical staining of control plant homogenates (NM carbon black - carbon black without fuel additive, A carbon black -with newly-invented fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and Cu compounds);
- SOD superoxide dismutases
- Figure 7 presents the graph of fuel additive composition optimization - cubic model verification
- Figure 8 presents TGA and DSC thermograms of carbon black and carbon black with fuel additive samples
- Figure 9 presents the DP thermogram (red line - DSC, black line - TGA);
- Figure 10 presents the thermovision image of Hercules auxiliary furnace (upon 8h from ignitron), whereas Figure 11 presents the thermovision image of SAS MI fine-coal auxiliary furnace (upon 10 hours from ignition).
- the subject-matter of the invention is presented by the following examples of embodiment. Example 1.
- the fuel additive Upon mixing the components the fuel additive was obtained.
- the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 8 times, comparing to analogous combustion conditions without the additive. Thanks to this the chimney heat losses were reduced and fuel consumption was decreased. Soot deposited on the heat exchanger has lower carbon content and higher mineral component content (fly ash), comparing to carbon black produced during fuel consumption without the fuel additive.
- Application of fuel additive enables easier removal of deposits from heat exchanger. In addition it was observed that application of fuel additive reduces emission of nitrogen oxides in the flue gas.
- Carbon black composition on the basis of elementary analysis was as follows:
- Carbon black produced upon combustion of coal with no additives 50.54% in weight of coal
- Carbon black upon application of fuel additive coal 39.60% in weight, hydrogen 10.92% in weight, nitrogen 5.39% in weight.
- Carbon black composition upon application of commercially available fuel additive based on CuS0 4 and NaCl coal 44.66%, hydrogen 7.47%, nitrogen 5.01% (in weight).
- the remaining components include non-organic matter ( fly ash).
- the fuel additive was obtained.
- the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity.
- Quantity of carbon black covering the heat exchanger decreased 8 times, thanks to which the chimney heat losses were reduced and fuel consumption was decreased.
- Soot deposited on the heat exchanger has lower carbon content and higher mineral component content ( fly ash), comparing to carbon black produced during fuel consumption without the fuel additive, which enabled easier removal of deposits from heat exchanger.
- application of fuel additive reduces emission of nitrogen oxides in the fumes.
- the fuel additive was obtained.
- the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 5 times.
- the fuel additive was obtained.
- the additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 5 times.
- the other types of carbon black used in the description include:
- carbon black with fuel additive available on the market is based on NaCl and copper (name not provided on purpose).
- the additive according to the invention in contrary to the other additives available on the market, is based on iron compounds, more environmental friendly comparing to copper compounds demonstrating specific toxicity to environmental microflora.
- the flasks with BSM nutrient medium and relevant type of carbon black were placed in the batch retort. After sterilization one of each type of the flasks with relevant type of carbon were left as control sample (no bacteria), whereas the remaining two containing the same type of carbon black were filled with the same amount of cells of one of two bacterial strains (A or B, the principle of standardization of the number of cells in inoculum was described in Example 6). The cultures were kept in darkness to prevent possible photolysis of sample components and incubated for 4 weeks (30 2 C, RPM 150). The test was repeated 10 times.
- control samples i.e. containing the relevant type of carbon black however with no bacteria added, were filtered. All residues on the filters and weighted portions of carbon black were analyzed using the Headspace Gas Chromatography/Mas s Spectrometry (HS-GC-MS) after app. 15 minutes of vials thermostating in temperature 150 2 C directly before inoculation (50 ⁇ ).
- the dispenser temperature was set to 250 2 C, carrier gas stream proportion (helium) was 10: 1, column flow was 1 ml/min, whereas linear speed amounted to 36 cm/sec.
- the analysis used the programmable temperature change method: 60 2 C for 1 minute, temperature increase by 10 2 C/minute until the maximum temperature of 250 2 C (maintained for 1 minute) was reached.
- the tested plant was thale cress (Arabidopsis thaliana).
- Arabidopsis thaliana is a model plant commonly used in genetic tests (known genome) as well as biochemical, physiological and toxicological tests (certain standards in the area of assessment of different pollutants' phytotoxicity, including PAH recommend this species).
- genetic tests known genome
- biochemical, physiological and toxicological tests certain standards in the area of assessment of different pollutants' phytotoxicity, including PAH recommend this species.
- the plant was subject to the activity of three types of carbon black:
- Arabidopsis thaliana seeds were sterilized as follows in the eppendorf test-tube:
- the plants cultivated on the nutrient medium with B carbon black featured weaker growth among the plants treated with three types of carbon blacks.
- average height of A. thaliana cultivated in presence of this carbon black decreased along with its increasing concentration in the nutrient medium, in effect of which upon 14 days, at the highest concentration of carbon black, the plant height exceeded the control plants only by 5%.
- composition of the most important group of photosynthetic pigments i.e. chlorophyll a, b and carotenoids. These pigments are necessary for proper course of photosynthesis and condition the effective conversion of luminous energy into hydrocarbons. Pigments deficiencies or irregularities in their proportion decrease the photosynthetic efficiency and therefore widely-understood plant production.
- Pigment content was measured in four-week leaves of A. thaliana by sampling 4 leaves from each plant, homogenization and extraction of pigments with 80% (v/v) acetone solution.
- absorbance of the obtained extract was measured using the Jasco V-650 spectrophotometer at the following wavelengths: 662nm, 645nm and 470nm (Lichtenthaler method, 1987):
- the additive according to the invention stimulates plant photosynthetic pigment production, including valuable for health carotenoids, which is advantageous in context of plant growth, productivity and nutritive values.
- e) impact of carbon black on anti-oxidative enzymes activity Impact of A, B and NM carbon blacks on the activity of anti-oxidative enzymes was studied on 8-week plants.
- the tested enzymes were superoxide dismutases (SOD), being the metalloproteins protecting the cellular structures against oxidative stress. Depending on the bonded co-factor, they may have the form of copper/zinc, iron or manganese dismutases.
- SOD superoxide dismutases
- A. thaliana contains the genes of all the above-mentioned forms.
- Copper/zinc dismutases CuZnSOD are localized primarily in the chloroplasts, peroxisomes and cytosol, whereas Iron dismutases (FeSOD) are present in chloroplasts and manganese dismutases (MnSOD) in mitochondria and peroxisomes (K Kunststoffenstein et al. 1998, Malecka & Tomaszewska 2005). Enzyme activity was tested using the native electrophoresis with histochemical staining method. Electrophoresis was carried out on polyacrylamide gels (11.6% (bottom) and 0.8% (upper)) at 180V in 4°C. Upon electrophoresis, the gels were subject to 30-minute staining to detect SOD activity (Miszalski et al. 1998).
- the additive according to the invention applied in the production of carbon black A does not increase the oxidative stress in plant cells, both in plants not treated with carbon black (control) and growing in presence of carbon black produced with no additive.
- Experiments #1-10 result from the experiment plan (simplex plan, grade 3 ⁇ 3;3 ⁇ ).
- Experiments #11 and 12 were used to develop a mathematical model and optimize the experiment towards the extreme (minimum) of the objective function, physical sense of which corresponds to the lowest coverage of heat exchanger with deposited soot.
- Fig. 7 presents the graph illustrating that the lowest coverage of heat exchanger is obtained when the chemical composition of the additive ranges between points #4, 5, 10 and 11.
- f ( ) 48.90x+37.76y+36.13z-82.40xy-89.06xz-42.61yz+27.38xyz-81.30xy(x-y)- -93.15xz(x-z)+90.22yz(y-z) (formula 1)
- Fig. 8 features the thermogravimetric analysis curves and differential scanning calorimetry (DSC) analysis curves, performed for the carbon black samples (black line) and carbon black with fuel additive (red line).
- DSC differential scanning calorimetry
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
The invention concerns the ecological fuel additive, composed of triferric tetroxide, nitrates containing 30-60% in weight of triiron tetroxide (Fe3O4), 10-30% in weight of potassium nitrate(V) (KNO3), sodium nitrate (V) (NaNO3), ammonium nitrate(V) (NH4NO3), or mixture of the abovementioned nitrates(V), 5-30% in weight of sodium percarbonate (Na2CO3⋅1.5H2O2) and 10% in weight of anti-caking agent. Advantageously, the anti-caking agent is powdered burnt clay and Fe3O4 used for production of fuel additive is free from FeSO4. The solid fuel additive according to the invention is ecological thanks to this that the production of carbon black and toxic compounds present in carbon black is reduced.
Description
Ecological solid fuel additive, reducing soot formation
The subject-matter of the invention is the ecological solid fuel additive, reducing soot formation. The fuel additive for soot combustion applied in operations of hard coal, lignite, fine coal, coke, anthracite, peat, pellets, coal briquettes and wood-burning furnaces as well as low, medium and high efficiency furnaces and boilers.
To this moment, the fuel additives, chemical composition of which could produce corrosion of steel and ceramic components of the heating installation or contribute to increased release of toxic pollutants formed in the combustion process, have been used.
There are certain fuel additives containing the mixtures of inorganic and organic soils, primarily chlorides and transition metal compounds, for the most copper, known.
The effective fuel additive allowing for reduction by deposit volume at the exchanger by 45- 55% is known from the Chinese patent CN 1010483. The fuel additive is a mixture of potassium nitrate (60-80%), ammonium nitrate, triiron tetroxide (0.1-1.0%), charcoal, borax, trisodium phosphate as chelating agent, magnesium, aluminum, sodium chloride and powdered sulphur. The additive is used in household and industrial installations and industrial coal-burning boilers. The additive modifies chemical and physical soot properties improving at the same time heating efficiency of the heat exchanger. The fuel additive is decomposable in 485°C, forming a coating on the heat exchanger surface and protecting it against corrosion. Coal additive to coal of low calorific value known from the Chinese CN 103305313 patent description contains 20-100% of active substance. Mixture of active substances contains 30- 80% in weight of calcium cobaltite (Ca3Co409), 0-30% in weight of triiron tetroxide (Fe304) and cerium dioxide (Ce02) and potassium oxide of several percents in weight. The fuel additive revealed in this invention decreases the fuel ignition temperature by 3-15°C, enhancing the combustion effectiveness and making coal combustion with fuel additive less polluting to the air comparing to fuel combustion without the fuel additive.
The soot combustion catalysts containing copper sulphate, sodium chloride and ammonium chloride are known from PL 207482 and PL 165406 patent description. Despite its advantages in combustion of lesser quantities of coal and lower risk of carbon deposities ignition in the flue pipes, this is not environmentally safe operation.
The ecological aquous liquid fuel additive containing among others hydrated fusel oils and ethyl alcohol is known from Polish patent PL 202335.
The solid biomass additive containing among others the carboxylic acid salts and one or more metals from among the alkaline earth, lanthanide and ferrous metals; fatty acid esters and fatty
acids or acidic resins, is known from the EP 0 725 128 B l patent. The fatty acid esters are, advantageously, methyl esters, in particulars of rape oil esters. The described additive enhances mechanical properties of biomass in the course of processing and reduces production of toxic fumes. The disadvantage of the described solution is no opportunity to apply the additive to any other fuels than pulverized one.
Known fuel additives may be harmful to the environment (copper and chlorine compounds), cause excessive corrosion of boiler and flue pipes (chloride and sulphur compounds, fatty acid oxy-degradation products) and have pathogenic effect (cerium compounds).
Despite numerous research and attempts to solve the problem of ecological fuel combustion and soot formation, smog and damages to the environment, the quest for enhanced additive ensuring more effective and safer to the environment fuel consumption has been continued.
The subject-matter of the invention is the ecological solid fuel additive, composed of triiron tetroxide, nitrates, most frequently potassium nitrate(V) containing 30-60% in weight of triiron tetroxide (Fe304), 10-30% in weight of potassium nitrate(V) (KN03), sodium nitrate(V) (NaN03), ammonium nitrate(V) (NH4N03), or mixture of the abovementioned nitrates(V), 5-30% in weight of sodium percarbonate (Na2C03- 1,5H202) and 10% in weight of anti-caking agent.
Advantageously, the anti-caking agent is powdered burnt clay.
Advantageously, Fe304 used for fuel additive production is free from FeS04.
Advantageously, soot production and toxic compounds present in soot is limited.
Ecological solid fuel additive reducing soot production presented in the invention is a proposal for environment-friendly solid fuel combustion, preventing environmental contamination with soot accompanying pollutants such as: polyaromatic hydrocarbons (PAH), persistent organic radicals and heavy metals, whereas reduction of carbon black production prevents additionally the excessive fuel consumption (carbon black decreases the heating efficiency of a boiler) and increases combustion effectiveness.
Solid fuel additive according to the invention is characterized by that it contains 30-60% in weight of triiron tetroxide (Fe304), 10-30% in weight of potassium nitrate(V) (KN03), sodium nitrate(V) (NaN03), ammonium nitrate(V) (NH4N03), or mixture of the abovementioned nitrates(V), 5-30% in weight of sodium percarbonate (Na2C03- 1,5H202) and 10% in weight of anti-caking agent e.g. powdered burnt clay.
It is important that Fe304 used for fuel additive production is free from FeS04 (FeS04 may act as the raw material for Fe304 production, which explains its presence). FeS04 presence in small quantities does not change the activity of fuel additive towards reducing the carbon black production, however carbon black obtained in presence of even small quantities of FeS04 is significantly less biodegradable (negative environmental impact).
The additive according to the invention, introduced to the combustion chamber with fuel or at the surface of the combusted fuel, is subject to partial thermal decomposition and releases the larg volume of gaseous products. Fuel additive components are activated in the temperature range of 80-650°C. Gaseous products of nitrates and sodium percarbonate decomposition reaction transport part of Fe304 quantity onto the carbonaceous deposite surface covering the heat exchanger. Fe304 particles in contact with heated fuel reach high temperature and then are transported on the carbonaceous deposite surface along with flue gas, where using its energy and catalytic oxidation properties catalyze the reaction of complete and total fuel combustion for hours.
Thermal decomposition of nitrates(V) is connected with production of atomic oxygen, which, at the moment of production (in statu nascendi) is highly reactive thanks to which it may easily oxidize the carbon black deposits covering the heat exchanger.
Decomposition of sodium percarbonate produces the peroxide and hydroxyl radicals, which, by means of chain reactions, are able to initiate the carbon black oxidation reaction.
Advantageously, application of fuel additive results in significant lowering of carbon black oxidation temperature. When applying the said fuel additive, carbon black, thanks to lowering the energy of oxidation initiation in low-oxygen atmosphere, begins combustion in temperature of 300°C, whereas in the process without added fuel additives this temperature is >700°C.
Apart from decreasing the quantity of carbon black produced in the fuel combustion process, the chemical composition of the produced carbon black changes advantageously, in effect of which it contains less harmful substances. Modification of the composition in result of application of the ecological fuel additive facilitates biodegradation of substances contained in the carbon black, including cancerogenic polyaromatic hydrocarbons (PAH).
The additive according to the invention should be used in quantity of 0.5-2 kg per 1000 kg of fuel, advantageously 1.2 kg per 1000 kg of fuel in the case of application of additive in mixture with fuel. Chemical composition of the additive is decisive for its value, however its dose i.e. weight proportion of the additive to fuel unit (1000 kg) is almost of equal
importance. During periodical application, the sufficient quantity is 50 g of additive in weekly intervals. In the cases of tendency of the heat exchanger to intensive covering with deposite resulting from quality of combusted fuel or the structure of heating installation, it is necessary to increase the fuel additive dose or its more frequent application.
Thanks to the fact that the ferrous compounds, in opposite to copper compounds, are not as toxic to the environment, the additive and produced carbon black is more environment- friendly. Combustion is more complete and produces less waste and smaller quantities of carbon black, which is additionally less toxic. There is also more energy produced. Solid fuel additive (coal, briquettes, etc.) according to the invention is a better ecological product than the additives in the composition, containing also: copper, chlorine, sulphur or fatty acids. The most significant pro-ecological effect of the fuel additive according to the invention is reduced carbon black production i.e. cancerogenic substance causing a greenhouse effect, carrier of polyaromatic hydrocarbons, stable organic radicals and heavy metals. Carbon black is also a pathogenic agent (circulatory and respiratory system diseases). Carbon black is a chemical and physical pollutant of air, water and soils, therefore its reduction constitutes a significant component of air protection programmes as well as the low emission reduction programmes (LERP). It is known that soot is a powerful absorbent of sunlight and contributes to climate warming and melting of glaciers covered with so called dry deposition (particulates) causing the greenhouse effect. Ecological effect of the additive according to the invention results also in lowering the combustion temperature and quantity of produced combustion gases, whereas the limited amount of produced soot is both less toxic and its components are biodegradable, and demonstrates the properties stimulating plant growth, including biomass increase.
To summarize, upon application of fuel additive according to the invention, less carbon black is produced, and the produced carbon black has different composition comparing to carbon black produced upon application of commercially available fuel additives or without their application, which makes it significantly less toxic i.e. more ecological.
To illustrate the solution according to the invention, a figure was enclosed, on which:
Figure 1 presents comparison of the content of the total of 4 components of soot sample determined using the HS-GC-MS method in the soot biodegradtion studies of two carbon black types;
Figure 2 presents the impact of carbon black (5% v/v) on the rate of occurrence of visible cotyledons of A. thaliana. NM carbon black - carbon black without fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
Figure 3 presents the impact of carbon black (5% v/v) on the rate of occurrence of the first leaf pair of A. thaliana. NM carbon black - carbon black without fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
Figure 4 presents the impact of the studied types of carbon black (5% v/v) on mass increase of A. thaliana upon 2 and 4 weeks of cultivation. NM carbon black - carbon black without fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A soot - carbon black with fuel additive according to the invention;
Figure 5 presents the impact of the tested soot types (5% v/v) on pigment content in A. thaliana upon 4 weeks of cultivation. NM carbon black - carbon black without fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and copper, A carbon black - carbon black with fuel additive according to the invention;
Figure 6 presents the graph of A. thaliana superoxide dismutases (SOD) activity upon native electrophoresis and histochemical staining of control plant homogenates (NM carbon black - carbon black without fuel additive, A carbon black -with newly-invented fuel additive, B carbon black - carbon black with added commercially available additive containing significant quantities of NaCl and Cu compounds);
Figure 7 presents the graph of fuel additive composition optimization - cubic model verification;
Figure 8 presents TGA and DSC thermograms of carbon black and carbon black with fuel additive samples;
Figure 9 presents the DP thermogram (red line - DSC, black line - TGA);
Figure 10 presents the thermovision image of Hercules auxiliary furnace (upon 8h from ignitron), whereas Figure 11 presents the thermovision image of SAS MI fine-coal auxiliary furnace (upon 10 hours from ignition).
The subject-matter of the invention is presented by the following examples of embodiment. Example 1.
The additive containing the following was obtained:
triiron tetroxide 45 parts by weight
sodium percarbonate 30 parts by weight
potassium nitrate 15 parts by weight
powdered burnt clay 10 parts by weight
Upon mixing the components the fuel additive was obtained. The additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 8 times, comparing to analogous combustion conditions without the additive. Thanks to this the chimney heat losses were reduced and fuel consumption was decreased. Soot deposited on the heat exchanger has lower carbon content and higher mineral component content (fly ash), comparing to carbon black produced during fuel consumption without the fuel additive. Application of fuel additive enables easier removal of deposits from heat exchanger. In addition it was observed that application of fuel additive reduces emission of nitrogen oxides in the flue gas.
Example 2.
Carbon black composition
Carbon black composition on the basis of elementary analysis was as follows:
Carbon black produced upon combustion of coal with no additives: 50.54% in weight of coal,
7.93% in weight of hydrogen and 4.65% in weight of nitrogen.
Carbon black upon application of fuel additive: coal 39.60% in weight, hydrogen 10.92% in weight, nitrogen 5.39% in weight.
Carbon black composition upon application of commercially available fuel additive based on CuS04 and NaCl: coal 44.66%, hydrogen 7.47%, nitrogen 5.01% (in weight).
The remaining components include non-organic matter ( fly ash).
Example 3.
The additive containing the following was obtained:
triiron tetroxide 45 parts by weight
sodium percarbonate 30 parts by weight
potassium nitrate 15 parts by weight
powdered burnt clay 10 parts by weight
Upon mixing the components the fuel additive was obtained. The additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 8 times, thanks to which the chimney heat losses were reduced and fuel consumption was decreased. Soot deposited on the heat exchanger has lower carbon content and higher mineral component content ( fly ash), comparing to carbon black produced during fuel consumption without the fuel additive, which enabled easier removal of deposits from heat exchanger. In addition it was observed that application of fuel additive reduces emission of nitrogen oxides in the fumes.
Example 4.
The additive containing the following was obtained:
triiron tetroxide 30 parts by weight
sodium percarbonate 20 parts by weight
potassium nitrate 40 parts by weight
powdered burnt clay 10 parts by weight
Upon mixing the components the fuel additive was obtained. The additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 5 times.
Example 5.
The additive containing the following was obtained:
triiron tetroxide 30 parts by weight
sodium percarbonate 30 parts by weight
potassium nitrate 30 parts by weight
powdered burnt clay 10 parts by weight
Upon mixing the components the fuel additive was obtained. The additive was introduced onto the surface of combusted fuel in coal boiler of 29 kW capacity. Quantity of carbon black covering the heat exchanger decreased 5 times.
In the description of the biological tests the following expression was used:
'carbon black produced in result of combustion with fuel additive according to the invention', which means carbon black produced with the additive being the subject-matter of the invention.
The other types of carbon black used in the description include:
1. non-modified carbon black i.e. produced with no additive (catalyst);
2. carbon black with fuel additive available on the market, however based on NaCl and copper (name not provided on purpose). The additive according to the invention, in contrary to the other additives available on the market, is based on iron compounds, more environmental friendly comparing to copper compounds demonstrating specific toxicity to environmental microflora.
Biological interactions of carbon black produced in result of combustion with fuel additive according to the invention in solid-fuel burning boilers.
Example 6.
Studying the impact of carbon black produced in result of combustion with the invented fuel additive on soil bacteria
In conical flasks (labelled A and B) of 100 ml volume containing 50 ml sterile liquid nutrient medium LB MIX (Table 1) each, the culture of two common soil bacteria: Pseudomonas aeruginosa - flask A and Bacillus subtilis - flask B was established.
Table 1. Composition of liquid nutrient medium LB MIX used for bacteria culture (pH - 7.00)
The study on the impact of carbon black produced with the invented fuel additive and carbon black produced in result of combustion with no additive on common soil microorganisms - Pseudomonas aeruginosa and Bacillus subtilis. The study was performed for two concentrations (w/v) of carbon black in the nutrient medium i.e. 0.30% and 6.00%. All tests were repeated 10 times. In the case of both bacterial strains, regardless of type and concentration of carbon black, bacteria growth was observed. Thanks to the applied dilutions,
carrying-out of the quantitative tests was possible. Average number of grown bacterial cultures in each analyzed case at the highest dilution of the culture suspension was 9 + 4. With regard to the above, application of fuel additive according to the invention is advantageous, since despite higher efficiency of solid fuel combustion, including decreased carbon black quantity, toxicity of this carbon black to the tested soil microorganisms does not increase.
Example 7.
Testing the soil bacterial capacity for biodegradation of the selected toxic components of carbon black with the invented fuel additive.
The tests were carried out with the use of two types of carbon black (carbon black produced in result of combustion with the invented fuel additive and non-modified carbon black (NM carbon black)) as well as Pseudomonas aeruginosa (A) and Bacillus subtilis (B) bacteria. Samples of each type of carbon black were grinded carefully in the mortar and 0.20 g to each conical flask of 100 ml volume was weighted out. Then each flask was filled with 50 ml of BSM mineral nutrient medium containing no carbon source (Table 2).
Table 2. Composition of BSM mineral nutrient medium containing no carbon source (pH 7.00)
The flasks with BSM nutrient medium and relevant type of carbon black were placed in the batch retort. After sterilization one of each type of the flasks with relevant type of carbon were left as control sample (no bacteria), whereas the remaining two containing the same type of carbon black were filled with the same amount of cells of one of two bacterial strains (A or B, the principle of standardization of the number of cells in inoculum was described in Example 6). The cultures were kept in darkness to prevent possible photolysis of sample components and incubated for 4 weeks (302C, RPM 150). The test was repeated 10 times. Upon completion of cultivations, 15 μΐ was sampled from each solution and streaked on LB MIX agar medium to verify, whether the inoculated organisms survived the incubation period.
The remaining part of the solutions were filtered using the Buchner funnel under decreased pressure via hard filters (degree: 390, weight: 84 g/sq m), selected with regard to the most effective recovery of carbon black from the solutions and the materials, from which these were produced (possibly resistant to high temperature e.g. 1502C used in headspace (HS) technique, consisting in analysis of gas phase above the solid or liqid sample). The filters were placed in glass vials and left for drying in ambient temperature for 5 days and then closed tightly.
Analogously, the control samples i.e. containing the relevant type of carbon black however with no bacteria added, were filtered. All residues on the filters and weighted portions of carbon black were analyzed using the Headspace Gas Chromatography/Mas s Spectrometry (HS-GC-MS) after app. 15 minutes of vials thermostating in temperature 1502C directly before inoculation (50 μΐ). The dispenser temperature was set to 2502 C, carrier gas stream proportion (helium) was 10: 1, column flow was 1 ml/min, whereas linear speed amounted to 36 cm/sec. The analysis used the programmable temperature change method: 602 C for 1 minute, temperature increase by 102C/minute until the maximum temperature of 2502 C (maintained for 1 minute) was reached. The analyses were carried out with the use of capillary column HP-1 MS (Agilent Technologies) of 30 m length, 0.25 mm diameter and Ιμιη film thickness. The transfer line was maintained in temperature of 2502 C, MS source temperature was 2302C, whereas quadrupole temperature was 1502C and dwell time - 100 ms.
Cumulative content of phenol (m/z = 94, RT = app. 7.78 min.), naphtalene (m/z = 128; RT = app. 10.04 min.), phenanthrene (m/z = 178; RT = app. 17.67 min.) and anthracene (m/z = 178; RT = app. 17.79 min.) was determined in the samples. The results of determination of the total of 4 selected polyaromatic hydrocarbons demonstrate the changes in the carbon black structure (Fig. 1).
The phenol, naphthalene, phenanthrene and anthracene biodegradation rate without the fuel additives and with the ecological fuel additive was researched. The highest biodegradation rate of the determined pollutants was observed for the samples of carbon black produced with the use of additive according to the invention, with added P. aeruginosa (A) (77.9 + 3.2%), followed by B. subtilis (B) (40,2 + 2,8%). In the case of non-modified carbon black, this rate amounted to 59.7 + 2.7% for the culture with P. aeruginosa bacteria and 29.2 + 1.6% for B. subtilis, respectively. In addition, it was observed that the primary samples of carbon black
produced with fuel additive according to the invention contained significantly lower quantity of determined compounds comparing to non-modified carbon black.
Application of fuel additive according to the invention is thus advantageous, since higher efficiency of solid fuel combustion, including decreased carbon black quantity, is accompanied by lower amount of toxic compounds in the produced carbon black comparing to the carbon black produced with no additive, and these compounds are easier biodegradable by common soil bacteria and do not increase mortality of these bacteria.
Example 8.
Studying the impact on carbon black produced in result of combustion with the invented on the selected physiological - biochemical parameters of plants
The impact of carbon black produced with the invented fuel additive on such physiological - biochemical parameters of plants as:
a) seed germination;
b) plant growth,
c) biomass production,
d) photosynthetic pigment concentration;
e) anti-oxidative enzyme activity
was examined.
The tested plant was thale cress (Arabidopsis thaliana). Arabidopsis thaliana is a model plant commonly used in genetic tests (known genome) as well as biochemical, physiological and toxicological tests (certain standards in the area of assessment of different pollutants' phytotoxicity, including PAH recommend this species). Recently, the new methods of the use of this plant in the initial drug testing have been developed - to reduce the number of animal testing.
The plant was subject to the activity of three types of carbon black:
- carbon black produced with the invented additive (A carbon black);
- carbon black with the additive available on the market, produced with the use of sodium chloride and significant quantities of copper salt (B carbon black) (components present in vast majority of fuel additives available on the market);
- carbon black produced with no additive (NM carbon black).
The tests were carried out in sterile conditions, in vitro, and the plants were cultivated on the Gamborg B5 agar nutrient medium (Table 3).
Table 3. Composition of Gamborg B5 nutrient medium
Apart from control plants (not treated with carbon black), the plants were subject to the following concentrations of each of the tested carbon blacks: 1.25; 2.5; 5% (v/v) or only the highest of them.
Arabidopsis thaliana seeds were sterilized as follows in the eppendorf test-tube:
- seeds shaken for 1 minute in 70% ethanol solution;
- ethanol was eliminated and the seeds were treated in 10% ACE solution for 7 minutes with continuous mixing;
- upon elimination of ACE solution, the seeds were washed four times with sterile de- ionized water in the following sequence: lxlminute + 3x5 minutes.
Upon sterilization, 10 seeds were planted on the Gamborg 5B nutrient medium and upon germination, depending on the experiment, analyzed and/or transmitted to sterile jars with the same medium - two plants to each jar. The plants were cultivated in the light of 80 μιηο1·ιη -~2 s" 1 intensity and photoperiod of 14h of light/lOh of darkness.
a) carbon black impact on seed germination
In the first days of culture, seed germination rate and growth rate of control plant seedlings has not deviated significantly from the germination rate on the nutrient media containing carbon black, regardless of the type of applied carbon black (Fig. 2). One should emphasize that in the case of carbon black with the invented fuel additive, starting from the third day of the experiment, the percentage rate of the best-grown seedlings was the highest both among the tested carbon blacks and slightly exceeded the control cultures.
The similar results were obtained when analyzing further growth of seedlings. However the percentage rate of the plants treated with A and B carbon black was the lowest in the first day of occurrence of the first leaf pair among all analyzed samples, upon two days the percentage rate of plants with the formed first leaf pair among the plants treated with carbon black was the highest in the case of A carbon black (with additive according to the invention), and upon the next two days, the average experimental value did not differ from the value recorded for control, however the plants treated with A carbon black featured more repeatable values (their distribution was significantly narrower comparing to all tested samples, including the control sample) (Fig. 3).
Application of the additive according to the invention is advantageous, since the carbon black produced in the presence thereof both has no inhibiting effect on the number of germinated seeds and features properties stimulating growth of the young seedlings.
b) impact of carbon black on growth of overground parts of the plants
Growth of overground part of the plant was measured in 7th and 14th day of culture. The measurement was performed along the plant from the highest point of cotyledon or plant leaves, to the part of stem bordering the nutrient medium.
The results of the experiment demonstrating that the plants cultivated on the nutrient media containing A carbon black (with fuel additive according to the invention) reached the greatest height. This was also the only carbon black, increase of content of which in the nutrient medium resulted in the intensified growth of the plant. Upon 7 days of culture, average height of plants treated with carbon black produced in result of application of the fuel additive according to the invention, exceeded the control plants by, respectively:
- 17% at 1.25% (v/v) content of carbon black in the nutrient medium),
- 37% (at 2.5% (v/v) content of carbon black in the nutrient medium)
- 60% (at 5% (v/v) content of carbon black in the nutrient medium).
Upon 14 days of the experiment, the plants cultivated on nutrient media containing A carbon black (with fuel additive according to the invention) reached greater height. Average height of plants treated to NM carbon black, at the highest content of this carbon black in the nutrient medium (5% v/v), was higher from control plants (not treated with carbon black) by 55%. However, upon the next 7 days, growth rate of plants subject to the highest concentration of this carbon black decreased significantly and these plants exceeded the control plants only by app. 35%, whereas the plants treated with carbon black with the additive according to the invention exceeded the control plants by 70% and remained the highest plants among all plants tested in the experiment.
The plants cultivated on the nutrient medium with B carbon black (produced with the commercially available fuel additives), however higher than the control plants, featured weaker growth among the plants treated with three types of carbon blacks. In addition, average height of A. thaliana cultivated in presence of this carbon black decreased along with its increasing concentration in the nutrient medium, in effect of which upon 14 days, at the highest concentration of carbon black, the plant height exceeded the control plants only by 5%.
Application of the additive according to the invention is advantageous, since carbon black produced in the presence thereof, in the case of growth of green parts of the plant, demonstrates clear fertilizing properties.
c) impact of carbon black on biomass production
The results of the experiment demonstrated that both upon two and four weeks of observation among the plants treated with carbon black, the highest average mass (converted into single plant) was recorded in plants growing in presence of carbon black A (with the additive according to the invention). Average mass of these plants at lower concentrations of carbon black A (1.25% and 2.5%) was in all tested types of carbon black the most approximated to mass of control plants, however, as in the case of each type of carbon black, lower than the control value. For the highest concentration of carbon black A (5% v/v), mass of tested plants upon 4 weeks of the experiment exceeded the mass of control plants by more than 30% (Fig. 4).
It is advantageous to use the additive according to the invention, since the carbon black produced in the presence thereof demonstrates visible fertilizing properties in plant biomass production. d) impact of carbon black on photosynthetic pigments content
Composition of the most important group of photosynthetic pigments, i.e. chlorophyll a, b and carotenoids, was analyzed. These pigments are necessary for proper course of photosynthesis and condition the effective conversion of luminous energy into hydrocarbons. Pigments deficiencies or irregularities in their proportion decrease the photosynthetic efficiency and therefore widely-understood plant production.
Pigment content was measured in four-week leaves of A. thaliana by sampling 4 leaves from each plant, homogenization and extraction of pigments with 80% (v/v) acetone solution.
To calculate the pigment content, absorbance of the obtained extract was measured using the Jasco V-650 spectrophotometer at the following wavelengths: 662nm, 645nm and 470nm (Lichtenthaler method, 1987):
CchiA = 11.75A662 - 2.35A645 [μ Ι ml of extract]
CchiB = 18.61Αβ45 - 3.96A662 l^g/l ml of extract]
ckar = (1000A470 - 2.27ccWA - 81.4ccWfc) : 227 [μ Ι ml of extract]
The obtained results were converted into pigment content in lg of fresh leaf mass (Fig. 5)
Excluding the plants growing in presence of carbon black with commercially available fuel additive (B carbon black), the proportions of individual pigments were correct. The plants growing in presence of B carbon black featured definitely deficient chlorophyll and carotenoids content, which may be decisive for their low productivity (low growth and biomass). The highest pigment content was observed in plants growing on the nutrient medium with carbon black with additive according to the invention (carbon black A).
The additive according to the invention stimulates plant photosynthetic pigment production, including valuable for health carotenoids, which is advantageous in context of plant growth, productivity and nutritive values. e) impact of carbon black on anti-oxidative enzymes activity
Impact of A, B and NM carbon blacks on the activity of anti-oxidative enzymes was studied on 8-week plants. The tested enzymes were superoxide dismutases (SOD), being the metalloproteins protecting the cellular structures against oxidative stress. Depending on the bonded co-factor, they may have the form of copper/zinc, iron or manganese dismutases. A. thaliana contains the genes of all the above-mentioned forms. Copper/zinc dismutases CuZnSOD) are localized primarily in the chloroplasts, peroxisomes and cytosol, whereas Iron dismutases (FeSOD) are present in chloroplasts and manganese dismutases (MnSOD) in mitochondria and peroxisomes (Kliebenstein et al. 1998, Malecka & Tomaszewska 2005). Enzyme activity was tested using the native electrophoresis with histochemical staining method. Electrophoresis was carried out on polyacrylamide gels (11.6% (bottom) and 0.8% (upper)) at 180V in 4°C. Upon electrophoresis, the gels were subject to 30-minute staining to detect SOD activity (Miszalski et al. 1998).
It was demonstrated that the plants treated with A carbon black presented no differences in context of isoform activity comparing to control plants and plants subject to NM carbon black. In all these plants, a dominating SOD isoform was iron dismutase (FeSOD). It was stated that in the plants treated with carbon black with additive according to the invention, as well as in plants treated with NM carbon black, activity of FeSOD isoform does not depend on carbon black concentration. Activity of the remaining isoforms i.e. MnSOD or CuZnSOD in plants treated with A carbon black, NM carbon black and control plants remains at similar and very low level, which makes the enzymatic profile of plants treated with A, NM carbon black and control plants in context of SOD activity identical (Fig. 6).
In the case of plants treated with B carbon black, a rapid increase in activity of copper/zinc forms was observed comparing to the control samples and plants cultivated with the two remaining types of carbon black (NM and A). CuZnSOD isoforms featured the highest activity, which increased along with increase of carbon black concentration in the nutrient medium. In plants treated with B carbon black a minor increase of MnSOD isoform activity was observed, whereas the activity of FeSOD isoform was comparable with activity in control extracts and plants subject to the remaining types of carbon black (NM and A) (Fig. 6).
The additive according to the invention applied in the production of carbon black A does not increase the oxidative stress in plant cells, both in plants not treated with carbon black (control) and growing in presence of carbon black produced with no additive.
The commonly applied and available on the market additive contributes to production of carbon black causing a harmful oxidative stress in plant cells reflecting in rapid increase of
activity of additional SOD isoforms, activity of which in the control plants and plants treated with NM and A carbon blacks was insignificant.
Application of ecological additive according to the invention is therefore advantageous, since in the presence thereof carbon black does not contribute to generation of oxidative stress in plant cells.
Description of the effects of fuel additive according to the invention in the research on low efficiency boiler
Impact of fuel additive depending on share of active substances on coverage with carbon black of the heat exchanger of coal-burning boiler of 29 kW capacity was researched. The research results are presented in Table 4.
A mathematical model describing coverage of heat exchanger with soot in function of fuel additive composition was developed (Fig. 7, formula 1). Temperature range, in which the fuel additive is active for carbon black oxidation was specified (Fig. 8) followed by temperature range, in which the fuel additive is subject to thermal reactions (Fig. 9). Measurements of temperature distribution in furnace of central heating boiler were performed, according to which the furnace temperature is sufficient to activate the fuel additive (Fig. 10).
Table 4. Optimization plan for the fuel additive composition (FA)
#11 15 10 20 0.76 15.08
#12 25 7 13 0.65 12.89
Impact of fuel additive composition on coverage of heat exchanger with carbon black was researched. Experiments #1-10 result from the experiment plan (simplex plan, grade 3 {3;3 }). Experiments #11 and 12 were used to develop a mathematical model and optimize the experiment towards the extreme (minimum) of the objective function, physical sense of which corresponds to the lowest coverage of heat exchanger with deposited soot.
Fig. 7 presents the graph illustrating that the lowest coverage of heat exchanger is obtained when the chemical composition of the additive ranges between points #4, 5, 10 and 11. f ( )=48.90x+37.76y+36.13z-82.40xy-89.06xz-42.61yz+27.38xyz-81.30xy(x-y)- -93.15xz(x-z)+90.22yz(y-z) (formula 1)
where:
x -Fe304 mass,
y - sodium percarbonate mass,
z- nitrate mass,
x+y+z=15g
Coverage of coal-burning boiler heat exchanger with carbon black with no added fuel additive was, in average, 76.8 + 8.4 g/m (n=5).
The new fuel additive reduces significantly the temperature of carbon black oxidation, which was presented on Fig. 8. Fig. 8 features the thermogravimetric analysis curves and differential scanning calorimetry (DSC) analysis curves, performed for the carbon black samples (black line) and carbon black with fuel additive (red line). In the case of carbon black sample, the temperature increase is accompanied with slow decrease in mass caused by organic compounds desorption. This process is of endothermic nature. In the case of carbon black with fuel additive, a clear exothermic effect is observed, which is proved by maximum on the DSC curve.
The thermal effect corresponding to carbon black oxidation in the sample containing the fuel additive is accompanied by significant mass reduction, proving the catalytic activity of fuel additive.
According to Fig. 9, complete activation of the new fuel additive takes place in temperature up to 650°C, therefore introduction of fuel additive when the boiler is well heated is advantageous. Inflow of adequate air quantity to the combustion chamber ensures relevant combustion temperature, which in low efficiency boilers may exceed even 1000°C (Fig. 10). In fine coal boiler, combustion temperature is slightly lower, however sufficient for thermal decomposition of the fuel additive (Fig. 11).
Intensive airflow via the combusted fuel results in blowing of heated catalyst particles away. Fe304 particles are transported along with fumes and transmitted at the surface of the heat exchanger, where the carbon black oxidation process takes place. Determinations of iron content in carbon black produced from fuel combustion and combustion of fuel with fuel additive demonstrate that carbon black produced in chemically - supported process has higher iron content.
Literature:
Kliebenstein D. J., Monde R., Last R.L., 1998. Superoxide dismutase in arabidopsis: an electric enzyme family with disparate regulation and protein localization. Plant Physiology, 118, 637-650.
Malecka A., Tomaszewska B., 2005. Reaktywne formy tlenu w komorkach roslinnych i enzymatyczne systemy obronne. Postepy Biologii Komorki, 32, 2, 311-325.
Miszalski Z, Slesak I, Niewiadomska E, Baczek-Kwinta R, Liittge U, Ratajczak R. 1998. Subcellular localization and stress responses of superoxide dismutase isoforms from leaves in the C3-CAM intermediate halophyte Mesembryanthemum crystallinum L. Plant, Cell and Environment 21 : 169-179
Lichtenthaler, H.K. 1987. Chlorophylls and carotenoids: Pigments of photosynthetic biomembranes. Methods Enzymol. 148:350-382.
Claims
1. Ecological solid fuel additive composed of triiron tetroxide, nitrates, most frequently potassium nitrate(V),
characterized in that it contains 30-60% in weight of triiron tetroxide (Fe304), 10- 30% in weight of potassium nitrate(V) (KN03), sodium nitrate(V) (NaN03), ammonium nitrate(V) (NH4N03), or mixture of the abovementioned nitrates (V), 5- 30% in weight of sodium percarbonate (Na2C03- 1,5H202) and 10% in weight of anti-caking agent.
2. Solid fuel additive, according to patent claim 1, characterized in that the anti-caking agent is the powdered burnt clay.
3. Solid fuel additive, according to patent claim 1, characterized in that Fe304 used for production of fuel additive is free from FeS04.
4. Solid fuel additive, according to patent claim 1, characterized in that production of carbon black and toxic compounds present in carbon black is reduced.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL413233A PL231237B1 (en) | 2015-07-23 | 2015-07-23 | Ecological additive for solid fuels, restricting formation of soot |
| PCT/IB2015/057335 WO2017013476A1 (en) | 2015-07-23 | 2015-09-23 | Ecological solid fuel additive, reducing soot formation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP3325581A1 true EP3325581A1 (en) | 2018-05-30 |
| EP3325581B1 EP3325581B1 (en) | 2020-01-29 |
Family
ID=54360491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP15787013.0A Active EP3325581B1 (en) | 2015-07-23 | 2015-09-23 | Ecological solid fuel additive, reducing soot formation |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3325581B1 (en) |
| PL (1) | PL231237B1 (en) |
| WO (1) | WO2017013476A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907899A (en) * | 2022-06-10 | 2022-08-16 | 南方电网电力科技股份有限公司 | Composite decoking agent for household garbage incineration boiler |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL111802B2 (en) | 1976-11-25 | 1980-09-30 | Ckd Praha | Electric driving and independent regenerative braking system for power vehicles |
| PL207482A1 (en) | 1978-06-07 | 1980-01-28 | Maszyn Dla Fabryk Domow Zremb | |
| CN1010483B (en) | 1987-12-19 | 1990-11-21 | 北京市石景山科达技术研究所 | High efficient and rapid cleaner for smoke dirt and formulation thereof |
| PL165406B1 (en) | 1991-05-10 | 1994-12-30 | Katarzyna Gwardiak | Catalyser for use in combustion of carbon black |
| SE509025C2 (en) | 1995-01-23 | 1998-11-30 | Bycosin Ab | Substance for addition to solid biofuels |
| CN1215152C (en) * | 2001-12-15 | 2005-08-17 | 宋伟国 | Coal burning fortifying and regulating agent, its making method and application method |
| CN101665735A (en) * | 2008-09-01 | 2010-03-10 | 埃文·里普斯丁 | Combustion catalyst |
| CN103305313B (en) | 2013-07-09 | 2014-06-04 | 安徽建筑大学 | Combustion catalyst for low-heat value coal |
-
2015
- 2015-07-23 PL PL413233A patent/PL231237B1/en unknown
- 2015-09-23 EP EP15787013.0A patent/EP3325581B1/en active Active
- 2015-09-23 WO PCT/IB2015/057335 patent/WO2017013476A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114907899A (en) * | 2022-06-10 | 2022-08-16 | 南方电网电力科技股份有限公司 | Composite decoking agent for household garbage incineration boiler |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3325581B1 (en) | 2020-01-29 |
| PL231237B1 (en) | 2019-02-28 |
| WO2017013476A1 (en) | 2017-01-26 |
| PL413233A1 (en) | 2017-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Saleem et al. | Impact of lead tolerant plant growth promoting rhizobacteria on growth, physiology, antioxidant activities, yield and lead content in sunflower in lead contaminated soil | |
| Gonçalves et al. | The effect of increasing CO2 concentrations on its capture, biomass production and wastewater bioremediation by microalgae and cyanobacteria | |
| Andrey et al. | The role of biochar-microbe interaction in alleviating heavy metal toxicity in Hordeum vulgare L. grown in highly polluted soils | |
| Madhaiyan et al. | Metal tolerating methylotrophic bacteria reduces nickel and cadmium toxicity and promotes plant growth of tomato (Lycopersicon esculentum L.) | |
| Mann et al. | Biogas-conditioning with microalgae | |
| Huang et al. | Current techniques of growing algae using flue gas from exhaust gas industry: a review | |
| Keuth et al. | Biodegradation of phenanthrene by Arthrobacter polychromogenes isolated from a contaminated soil | |
| CN106147778A (en) | Passivator, preparation method and applications for repairing heavy metal in soil combined pollution | |
| Wu et al. | Cd immobilization mechanisms in a Pseudomonas strain and its application in soil Cd remediation | |
| Elahi et al. | Multiple metal resistance and Cr6+ reduction by bacterium, Staphylococcus sciuri A-HS1, isolated from untreated tannery effluent | |
| Liu et al. | Effect of a newly isolated native bacteria, Pseudomonas sp. NP22 on desulfurization of the low-rank lignite | |
| Ashokkumar et al. | Bioenergy production and metallic iron (Fe) conversion from Botryococcus sp. cultivated in domestic wastewater: Algal biorefinery concept | |
| CN111808754A (en) | Mining area soil microalgae and separation and purification method and application thereof | |
| Şener et al. | Fungal treatment of lignites with higher ash and sulphur contents using drum type reactor | |
| Taştan et al. | A novel coal additive from microalgae produced from thermal power plant flue gas | |
| Macek et al. | Accumulation of cadmium ions by hairy root cultures | |
| Yasin et al. | Effect of Bacillus fortis 162 on growth, oxidative stress tolerance and phytoremediation potential of Catharanthus roseus under chromium stress. | |
| CN107893047A (en) | One plant of oil fragrance surfactant hydrocarbon degradation bacteria and its application | |
| EP3325581B1 (en) | Ecological solid fuel additive, reducing soot formation | |
| Kailasan et al. | Isolation and characterization of Ralstonia pickettii-A novel phosphate solubilizing bacterium from Pomegranate rhizosphere from Western India | |
| Boynazarov et al. | Production of bentonite and humus natural organic substances from fluoride compounds | |
| Omar | Adsorption of zinc ions by Scenedesmus obliquus and S. quadricauda and its effect on growth and metabolism | |
| Kumari et al. | Impacts of cadmium and manganese on in vitro seed germination and seedling growth of horsegram | |
| Ji et al. | Research advances in organophosphorus pesticide degradation: a review | |
| Hale | Biochar and plant growth promoting Rhizobacteria as soil amendments |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20180220 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) | ||
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| 17Q | First examination report despatched |
Effective date: 20190401 |
|
| GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20190822 |
|
| GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
| GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE PATENT HAS BEEN GRANTED |
|
| AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1228504 Country of ref document: AT Kind code of ref document: T Effective date: 20200215 |
|
| REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602015046100 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20200129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200621 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200429 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: RS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 |
|
| REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200529 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200430 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 602015046100 Country of ref document: DE |
|
| REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 1228504 Country of ref document: AT Kind code of ref document: T Effective date: 20200129 |
|
| PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
| 26N | No opposition filed |
Effective date: 20201030 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 |
|
| REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
| GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200923 |
|
| REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200923 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200930 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200930 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200930 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200923 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200930 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200923 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BG Payment date: 20210921 Year of fee payment: 7 Ref country code: CZ Payment date: 20210914 Year of fee payment: 7 |
|
| PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20210915 Year of fee payment: 7 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 Ref country code: AL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20200129 |
|
| REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 602015046100 Country of ref document: DE |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CZ Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220923 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20230401 |
|
| PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20220923 |