US3514273A - Fuel oil additive - Google Patents
Fuel oil additive Download PDFInfo
- Publication number
- US3514273A US3514273A US778799A US3514273DA US3514273A US 3514273 A US3514273 A US 3514273A US 778799 A US778799 A US 778799A US 3514273D A US3514273D A US 3514273DA US 3514273 A US3514273 A US 3514273A
- Authority
- US
- United States
- Prior art keywords
- additive
- fuel oil
- oil
- magnesium
- boiler
- 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.)
- Expired - Lifetime
Links
- 239000003747 fuel oil additive Substances 0.000 title description 21
- 239000000654 additive Substances 0.000 description 46
- 230000000996 additive effect Effects 0.000 description 43
- 239000011777 magnesium Substances 0.000 description 29
- 229910052749 magnesium Inorganic materials 0.000 description 28
- 239000002245 particle Substances 0.000 description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 24
- 239000002253 acid Substances 0.000 description 22
- 229910052782 aluminium Inorganic materials 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 17
- 239000000295 fuel oil Substances 0.000 description 17
- 150000004679 hydroxides Chemical class 0.000 description 16
- 239000003921 oil Substances 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 239000004480 active ingredient Substances 0.000 description 11
- 239000002893 slag Substances 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- 239000002956 ash Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical class CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000004071 soot Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- IJCWFDPJFXGQBN-RYNSOKOISA-N [(2R)-2-[(2R,3R,4S)-4-hydroxy-3-octadecanoyloxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCCCCCCCCCCCC IJCWFDPJFXGQBN-RYNSOKOISA-N 0.000 description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000012717 electrostatic precipitator Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 229940067606 lecithin Drugs 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 2
- 235000011078 sorbitan tristearate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical class [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical class [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000803 paradoxical effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229950006451 sorbitan laurate Drugs 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 125000005287 vanadyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
-
- 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
-
- 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
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/191—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polyhydroxyalcohols
Definitions
- a fuel oil additive which is designed to reduce slagging, to facilitate removal of slag and like deposits from the fireside of boiler tubes, to reduce acid smut pollution, to eliminate low temperature. corrosion and to improve the electrical resistivity of particulate emission from a fuel oil flame, comprising a dispersion of finely divided particles or partially dehydrated hydroxides of magnesium and aluminum in a hydrocarbon oil.
- the invention is in the field of slag, acid smut pollution and low temperature corrosion inhibiting additives for fuel oil (acid smut is defined as carbon soot that has adsorbed S and becomes corrosive when cooled below acid dew-point temperature that may range from 350 F. to 140 F.).
- U. S. Pat. 3,002,826 proposes use of an additive in the form of an emulsion, the water phase of which is an aqueous solution of a salt of Al, B, Cu, Si or Zn, and the oil phase of which is a mineral oil.
- US. Pat. 3,067,018 relates to use of a specially formed emulsion of an oxide, hydroxide or carbonate of the metals of group II of the periodic system.
- US. Pat. 3,036,901 proposes the use of a finely divided, oil-insoluble metallic additive which is initially suspended in a hydrated calcium acetate gel before being blended with a residual fuel oil carrier.
- US. Pat. 2,845,338 proposes use of an additive comprising a mixture of a magnesium compound and a compound of Cu, Co, Mn, Fe or Ca.
- the invention broadly resides in a fuel oil additive which comprises a dispersion in a hydrocarbon oil of finely divided particles of partially dehydrated hydroxides of magnesium and aluminum in a petroleum oil containing an anionic or non-ionic surfactant, the weight ratio of magnesiumzaluminum being at least 1:1, said hy- "ice droxides having a minimum bound water content of about 0.5% by weight and a maximum bound water content of about 15% by weight.
- the additive of the invention may be applied to package or field-erected commercial, industrial, power utility and heat recovery boilers, as well as to many fuel oil fired processes.
- the additive when applied to a fuel oil in a suitable amount, has been found to (a) alleviate high temperature slagging and corrosion, (b) neutralize and dry up gummy, corrosive deposits at the cold end of a boiler or the like, (c) reduce the level of SO, and nitrogen oxides in the flue gases, (d) prevent the formation of acid smut, and (e) make it possible to control the emission of soot to the atmosphere.
- finely divided particles of partially dehydrated hydroxides of magnesium and aluminum are suspended or dispersed in a petroleum or hydrocarbon liquid carrier with an anionic or nonionic surfactant.
- the partially dehydrated hydroxides may be described as a compound mixture of oxides and hydroxides having the general formulae Mg OOH and Al QOH.
- the elemental magnesium present in the final mixture is not less than equal to the amounts of elemental aluminum in the mixture.
- a satisfactory Weight ratio of Mg:Al for most industrial applications is from 1:1 to about 10:1.
- the additive active ingredients should contain about 0.5 to about 15% by Weight of bound water. A restricted range of 0.5 to 5% by weight of bound water has been found to be quite satisfactory.
- the partially dehydrated hydroxide particles which range from 1 to 7 microns in size, are predominantly granular in shape to prevent erosion and plugging of fuel oil handling and atomizing equipment.
- the partially dehydrated hydroxide of magnesium is preferably obtained from sea or salt water because of its low abrasiveness and high chemical reactivity.
- the mentioned particle size acts to control the physical structure as well as the quantity of material that deposits in both hot and cold regions of the boiler. structurally, these particles are characterized by high specific surface areas varying from 400 to 1400 square meters per gram to maximize chemical reaction with combustion residues in gas, vapor and liquid state.
- the diameter of the pores permeating each particle should 'be at least 17 Angstroms and preferably range from 17 to 20 Angstrorns for optimum physical adsorption of gas-phase pollutants.
- the partially dehydrated hydroxides of the present invention have a physical structure completely different from that of the corresponding oxides and fully 'hydrated hydroxides.
- Aluminum oxide for instance, has a crystalline structure which is so abrasive as to render it quite unsuitable, from a practical point of view, as a fuel oil additive because of its destructive erosion effect on equipment such as pumps and the like. If the hydration is too great, stable suspensions of pumpable viscosities cannot be achieved with economical amounts of surfactant.
- the magnesium active ingredient of the present invention by virtue of its specific physical properties, readily reacts with and chemically neutralizes any condensed acid.
- the aluminum active ingredient increase the efiectiveness of any unreacted magnesium active ingredient that deposits on boiler surfaces by ensuring a highly porous (extended) surface layer for acid reac- 3 tions. Therefore, the net effect of using both magnesium and aluminum forms in the additive results in benefits due to the superposition of both physical adsorption and chemical neutralization processes.
- MgO additives gave poor results, while a fourth type produced good results.
- a probable explanation is that the fourth is smaller in particle size, thus offering a larger surface for reaction with oil ash sulfates of low-temperature boiling point.
- oil ash sulfates of low-temperature boiling point.
- MgO is available in the flame envelope where oil ash is greatest in concentration and turbulence is present for thorough mixing.
- no water is admitted with the MgO, as was the case with the slurry.
- the specified partially dehydrated hydroxides of the present invention are, as previously indicated, suspended or dispersed in a carrier liquid which is preferably a light hydrocarbon oil having a maximum viscosity of 35 SSU at 100 F.
- the surfactant which is anionic or non-ionic and compatible with both of the active ingredients and the hydrocarbon carrier, transforms the highly viscous, two-phase mixture into a free-flowing easily-pumpable suspension that blends readily with fuel oil.
- Suitable surfactants are readily available.
- the glycerol stearates and laurates and the heavy metal soaps of stearic, naphthenic and rosin acid are particularly suitable.
- specific surfactants are glycerol monostearate (as sold under the trade name Aldo 33 by Glycol Products Company); lecithin (as sold under the trade name Clearate by W. A.
- sorbitan monolaurate, sorbitan tristearate, and glycerol sorbitan laurate (as sold under the trade names Span 20, Span 65 and G-672, respectively, by Atlas Powder Company); fatty acid type such as that sold under the trade name TDO by Armour & Company; and heavy metal soaps, such as aluminum stearate, produced by reaction of a water soluble soap with a heavy metal salt of aluminum, magnesium, cobalt, zinc, manganese, or calcium.
- These surfactants also disperse and stabilize the solids in suspension by eliminating attractive forces on the particle surfaces.
- the surfactant is employed in concentrations ranging from 0.7% to 3.5% by weight.
- the specified bound water content range is quite significant. As this content approaches zero the viscosity decreases but below about 0.5 the water is diflicult to remove and the material becomes too expensive. Moreover, below about 0.5% desired physical characteristics are almost impossible to achieve. The product becomes diflicult to disperse, it may become erosive, and higher drying temperatures are needed.
- the final oil-base additive composition is a stable suspension having about 4060% by weight of the active additive ingredients and a viscosity of less than 115 SSU at F.
- Other physical characteristics may be listed as:
- the deposits produced when using the additive were subjected to an intensive thin section investigation to clarify the role of additive properties, such as mineral composition and physical state, in preventing slag formation.
- Microscopic examinations of deposit thin sections showed a thin, dense unsintered layer of sub-micron particles next to the tube surfaces.
- Subsequent deposits formed an intermediate upstream layer of friable, moderately porous material, an outer upstream layer having a thick, porous, wedge-shaped structure and an outer downstream layer of powdery, moderately porous, lightly sintered crystals.
- the partially dehydrated aluminum hydroxide component also plays two important roles in modifying the slag structure.
- alumina by reacting selectively with magnesia in the flame to form spinel, reduces the magnesia available for later reaction with sulphur oxides on the tube surface; this dictates the elemental magnesium to aluminum ratio for particular combustion conditions.
- the formation of magnesium sulphate, which is molten and sticky at 2050 F. should be minimized, particularly when gas tempertaures at the furnace exit are above 2100 F.; this is accomplished by increasing the aluminum active ingredient in the additive.
- the magnesia-alumina reaction product reduces the tendency of unreacted but superfine magnesia particles to agglomerate. This control over agglomeration is probably due to the presence of uniformly distributed spinel particles that form cubic crystals of octahedral shape.
- Porosity measurements on deposit samples also re vealed that high porosity and large voids were specific to partially dehydrated hydroxides of magnesium and aluminum having particle sizes ranging from 1 to 7 microns. Control of particle size is important because theoretical studies showed that particles larger than microns tend to form undesirably, densely impacted deposits. On the other hand, particles less than 0.5 micron tend to form undesirable cohesive deposits having small voids.
- the additive of the present invention is thus suitable for controlling slag deposits on boiler surfaces over a wide range of gas temperatures. Furthermore, by preventing slag formation on tube surfaces, high temperature oil ash corrosion becomes impossible so that tube temperatures may be safely maintained at 1100 F.
- the additive employed in the trials as described in this application was used at a dosage rate of 1 gallon of additive per 1500 gallons of fuel oil, and had the following specific formula and characteristic,
- this additive formulation (a) the hard, bonded slag build-up was replaced with a soft, friable powder that was easily removed by soot blowing, (b) bridging in the convection pass of the generating bank was eliminated, and (c) a light coating of additive oxides on the furnace walls was credited with raising superheat temperatures to design conditions for the first time.
- a shipboard trial has also been made with an additive as described above but with a magnesiumzaluminum ratio of about 1:1.
- Solids content percent by weight (a) 2500 F. gas temperature at the superheater,
- Solids content, percent by wt 7 Abatement of acid smut emission 7 Another benefit from using the fuel-oil additive invention has been the abatement of acid smut emission.
- acid smut, or soot soaked with sulphuric acid normally builds up in the cold end of a boiler or process and on the stack lining to some equilibrium thickness, after which it suddenly breaks free. Following emission to atmosphere these corrosive, sticky flakes of acid smut fall on people and property creating a seriousnuisance problem and, in some cases, considerable damage to fabrics, crops and automobile finishes.
- the fuel-oil additive described herein provides an economic means of controlling or eliminating boiler operational problems due to incombustible constituents in residual fuel oil. Economic benefits from using the additive include increased boiler availability and efliciency, reduced maintenance and fuel costs, and, in some cases, a financial credit on the sale of vanadium-rich ash collected in boiler and dust collector hoppers. Another major, but less tangible benefit, is the favourable public image created by minimizing the emission of noxious atmospheric pollutants.
- the additive which is normally metered continuously and automatically into the oil supply to each burner, can
- Additive dosage rates will vary according to fuel analysis and combustion conditions, but usually 1 gallon per 1500 gallons of fuel oil is sufficient to control most problems at the cold end of a boiler or the like.
- a fuel oil additive which comprises a dispersion of finely divided particles of partially dehydrated hydroxides of magnesium and aluminum in a petroleum oil containing an anionic or non-ionic surfactant, the weight ratio of magnesiumzaluminum being at least 1:1, said hydroxides having a minimum bound water content of about 0.5% by weight and a maximum bound water content of about 15% by weight.
- a fuel oil additive as defined in claim 1 said surfactant being selected from the group consisting of glycerol stearates and laurates, lecithin, fatty acids, and heavy metal soaps of stearic, naphthenic and rosin acids.
- a fuel oil additive as defined in claim 1 said particles being porous, the diameter of each pore in said particles being in the range of at least 17 angstrom units.
- a fuel oil additive as defined in claim 1 said particles being porous, the diameter of each pore in said particles being in the range of 17 to 2 0 angstrom units.
- a fuel oil additive as defined in claim 1 said particles having about 0.5 to 5% by weight of bound water.
- a method of preventing oil ash slagging, low temperature corrosion, acid smut emission, of reducing the level of S0 and nitrogen oxides in flue gases, chemically neutralizing and drying up gummy, corrosive deposits that form below acid dewpoint temperatures, in oil fired boilers comprising operating said boilers on a fuel oil containing about 1 gallon of additive in 1000 gallons of fuel oil to 1 gallon of additive in 2000 gallons of fuel oil, an additive comprising a petroleum oil having dispersed therein in the presence of an anionic or non-ionic surfactant 40 to 60% by weight of 1 to 7 micron particles of partially dehydrated hydroxides of Mg and Al having a minimum bound water content of about 0.5% by weight and a maximum bound water content of about 15% by weight, the weight ratio of magnesium:aluminum being at least 1:1.
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Description
United States Patent O 3,514,273 FUEL OIL ADDITIVE George K. Lee and Earland R. Mitchell, Ottawa, Ontario,
Canada, assignors to Canadian Patents and Develcpment Limited, Ottawa, Ontario, Canada, a corporation of Canada No Drawing. Continuation-impart of application Ser. No. 648,241, June 23, 1967. This application Nov. 25, 1968, Ser. No. 778,799
Int. Cl. C101 1/32 US. Cl. 44-51 13 Claims ABSTRACT OF THE DISCLOSURE A fuel oil additive, which is designed to reduce slagging, to facilitate removal of slag and like deposits from the fireside of boiler tubes, to reduce acid smut pollution, to eliminate low temperature. corrosion and to improve the electrical resistivity of particulate emission from a fuel oil flame, comprising a dispersion of finely divided particles or partially dehydrated hydroxides of magnesium and aluminum in a hydrocarbon oil.
CROSS REFERENCE TO RELATED APPLICATION This application is a continuation-in-part of Ser. No. 648,241, fi ed June 23, 1967, and now abandoned.
BACKGROUND OF THE INVENTION Field of the invention The invention is in the field of slag, acid smut pollution and low temperature corrosion inhibiting additives for fuel oil (acid smut is defined as carbon soot that has adsorbed S and becomes corrosive when cooled below acid dew-point temperature that may range from 350 F. to 140 F.).
Description of the prior art The use of fuel additives to prevent fouling and corrosion of gas turbine blades, and slag build-up, corrosion of both highand low-temperature heat transfer surfaces and the like in coal and oil fired boilers have. been the subject of research.
Proposals have been made for solution of gas turbine problems wherein conditions differ from those existing in coal and oil fired boilers. For instance, U. S. Pat. 3,002,826 proposes use of an additive in the form of an emulsion, the water phase of which is an aqueous solution of a salt of Al, B, Cu, Si or Zn, and the oil phase of which is a mineral oil. US. Pat. 3,067,018 relates to use of a specially formed emulsion of an oxide, hydroxide or carbonate of the metals of group II of the periodic system.
A proposal for solution of slag build-up in coal-fired boilers is the subject of US. Pat. 3,004,836 which relates to the use of a ground magnesia-phosphate mixture.
US. Pat. 3,036,901 proposes the use of a finely divided, oil-insoluble metallic additive which is initially suspended in a hydrated calcium acetate gel before being blended with a residual fuel oil carrier.
US. Pat. 2,845,338 proposes use of an additive comprising a mixture of a magnesium compound and a compound of Cu, Co, Mn, Fe or Ca.
SUMMARY OF THE INVENTION The invention broadly resides in a fuel oil additive which comprises a dispersion in a hydrocarbon oil of finely divided particles of partially dehydrated hydroxides of magnesium and aluminum in a petroleum oil containing an anionic or non-ionic surfactant, the weight ratio of magnesiumzaluminum being at least 1:1, said hy- "ice droxides having a minimum bound water content of about 0.5% by weight and a maximum bound water content of about 15% by weight.
The additive of the invention may be applied to package or field-erected commercial, industrial, power utility and heat recovery boilers, as well as to many fuel oil fired processes. The additive, when applied to a fuel oil in a suitable amount, has been found to (a) alleviate high temperature slagging and corrosion, (b) neutralize and dry up gummy, corrosive deposits at the cold end of a boiler or the like, (c) reduce the level of SO, and nitrogen oxides in the flue gases, (d) prevent the formation of acid smut, and (e) make it possible to control the emission of soot to the atmosphere.
DESCRIPTION OF THE PREFERRED EMBODIMENT In accordance with the invention, finely divided particles of partially dehydrated hydroxides of magnesium and aluminum are suspended or dispersed in a petroleum or hydrocarbon liquid carrier with an anionic or nonionic surfactant.
The partially dehydrated hydroxides may be described as a compound mixture of oxides and hydroxides having the general formulae Mg OOH and Al QOH. The elemental magnesium present in the final mixture is not less than equal to the amounts of elemental aluminum in the mixture. A satisfactory Weight ratio of Mg:Al for most industrial applications is from 1:1 to about 10:1. The additive active ingredients should contain about 0.5 to about 15% by Weight of bound water. A restricted range of 0.5 to 5% by weight of bound water has been found to be quite satisfactory.
The partially dehydrated hydroxide particles, which range from 1 to 7 microns in size, are predominantly granular in shape to prevent erosion and plugging of fuel oil handling and atomizing equipment. The partially dehydrated hydroxide of magnesium is preferably obtained from sea or salt water because of its low abrasiveness and high chemical reactivity. Moreover, the mentioned particle size acts to control the physical structure as well as the quantity of material that deposits in both hot and cold regions of the boiler. structurally, these particles are characterized by high specific surface areas varying from 400 to 1400 square meters per gram to maximize chemical reaction with combustion residues in gas, vapor and liquid state. The diameter of the pores permeating each particle should 'be at least 17 Angstroms and preferably range from 17 to 20 Angstrorns for optimum physical adsorption of gas-phase pollutants.
It is pointed out that the stated particle size, pore size,
and surface area are achieved by partially dehydrating the hydroxides of Mg and Al under closely controlled timetemperature conditions to the specified bound water content. It will be appreciated that the partially dehydrated hydroxides of the present invention have a physical structure completely different from that of the corresponding oxides and fully 'hydrated hydroxides. Aluminum oxide, for instance, has a crystalline structure which is so abrasive as to render it quite unsuitable, from a practical point of view, as a fuel oil additive because of its destructive erosion effect on equipment such as pumps and the like. If the hydration is too great, stable suspensions of pumpable viscosities cannot be achieved with economical amounts of surfactant.
The magnesium active ingredient of the present invention, by virtue of its specific physical properties, readily reacts with and chemically neutralizes any condensed acid. On the other hand, the aluminum active ingredient increase the efiectiveness of any unreacted magnesium active ingredient that deposits on boiler surfaces by ensuring a highly porous (extended) surface layer for acid reac- 3 tions. Therefore, the net effect of using both magnesium and aluminum forms in the additive results in benefits due to the superposition of both physical adsorption and chemical neutralization processes.
Although the present invention is based upon the particular development 'of an additive having specified characteristics, the general knowledge that the various oxides and hydroxides of Mg and Al vary greatly in physical structure and chemical reactivity have been well-recognized in the past.
For instance, a paper entitled Lilco Trims Residual Oil Problems (L. M. Exley, A. E. Tamburrino and A. J. Neal, Jr., Power Magazine, April 1966) reported that:
These experiences with MgO are somewhat paradoxical: Three types of MgO additives gave poor results, while a fourth type produced good results. A probable explanation is that the fourth is smaller in particle size, thus offering a larger surface for reaction with oil ash sulfates of low-temperature boiling point. And, since it is injected with the fuel oil, there is assurance that the MgO is available in the flame envelope where oil ash is greatest in concentration and turbulence is present for thorough mixing. Finally, no water is admitted with the MgO, as was the case with the slurry.
Another paper entitled Effect of Fuel Oil Additives on Oil-Ash Corrosion and Deposits (R. C. Amero, A. G. Rocchini and C. E. Trautman, ASTM Technical Committee, E Symposium, Ian. 28, 1964, Atlantic City, NJ.) shows that different forms of Mg and Al additives tested under nearly identical conditions yield widely divergent results. The paper contains the following data,
These papers show that both the mineral composition and physical structure of each magnesium additive strongly influence its ability to control deposits and corrosion due to residual oil ash, even though the various magnesium materials should, by elementary reasoning oxidizes in the flame and deposit as MgO. The tests given in the Amero et al. paper indicate corresponding results with two Al compounds.
The specified partially dehydrated hydroxides of the present invention are, as previously indicated, suspended or dispersed in a carrier liquid which is preferably a light hydrocarbon oil having a maximum viscosity of 35 SSU at 100 F.
.The surfactant, which is anionic or non-ionic and compatible with both of the active ingredients and the hydrocarbon carrier, transforms the highly viscous, two-phase mixture into a free-flowing easily-pumpable suspension that blends readily with fuel oil. Suitable surfactants are readily available. For example, the glycerol stearates and laurates and the heavy metal soaps of stearic, naphthenic and rosin acid, are particularly suitable. Examples of specific surfactants are glycerol monostearate (as sold under the trade name Aldo 33 by Glycol Products Company); lecithin (as sold under the trade name Clearate by W. A. Cleary Corporation); sorbitan monolaurate, sorbitan tristearate, and glycerol sorbitan laurate (as sold under the trade names Span 20, Span 65 and G-672, respectively, by Atlas Powder Company); fatty acid type such as that sold under the trade name TDO by Armour & Company; and heavy metal soaps, such as aluminum stearate, produced by reaction of a water soluble soap with a heavy metal salt of aluminum, magnesium, cobalt, zinc, manganese, or calcium. These surfactants also disperse and stabilize the solids in suspension by eliminating attractive forces on the particle surfaces. The surfactant is employed in concentrations ranging from 0.7% to 3.5% by weight.
The specified bound water content range is quite significant. As this content approaches zero the viscosity decreases but below about 0.5 the water is diflicult to remove and the material becomes too expensive. Moreover, below about 0.5% desired physical characteristics are almost impossible to achieve. The product becomes diflicult to disperse, it may become erosive, and higher drying temperatures are needed.
Above about 15% bound water content the viscosity is too great (approaching paste consistency), more surfactant is needed with consequent lack of economy, and it is diflicult to achieve economical loading of the additive.
The final oil-base additive composition is a stable suspension having about 4060% by weight of the active additive ingredients and a viscosity of less than 115 SSU at F. Other physical characteristics may be listed as:
Specific gravity at 70 F.l.35 Flash point (PM), F.l50 minimum Pour point, F.- 10 maximum Alleviation of high temperature deposits and corrosion Laboratory experiments, using a combustion rig closely simulating field conditions, have shown that the additive described is particularly elfective in changing the normally rock-like fuel ash slag into a porous, friable, powdery deposit that is easily removed by routine soot-blowing procedures. The deposit build-up with the use of the additive is loosely bonded to boiler tube surfaces and weakly agglomerated.
The deposits produced when using the additive were subjected to an intensive thin section investigation to clarify the role of additive properties, such as mineral composition and physical state, in preventing slag formation. Microscopic examinations of deposit thin sections showed a thin, dense unsintered layer of sub-micron particles next to the tube surfaces. Subsequent deposits formed an intermediate upstream layer of friable, moderately porous material, an outer upstream layer having a thick, porous, wedge-shaped structure and an outer downstream layer of powdery, moderately porous, lightly sintered crystals.
By optical and X-ray diffraction methods, it was determined that a magnesia-alumina reaction product, known as spinel, was uniformly distributed throughout all four layers and that the proportion of magnesium sulphate to magnesium oxide increased progressively toward the tube surface. The work also revealed that most of the vanadium was concentrated in the intermediate upstream and the outer downstream layers as bands of sodium vanadyl vanadate and magnesium orthovanadate. The partially dehydrated magnesium hydroxide component, therefore, prevents slagging of low-melting sodium and vanadium compounds by both mechanical dilution and chemical reaction.
The partially dehydrated aluminum hydroxide component also plays two important roles in modifying the slag structure. First, alumina, by reacting selectively with magnesia in the flame to form spinel, reduces the magnesia available for later reaction with sulphur oxides on the tube surface; this dictates the elemental magnesium to aluminum ratio for particular combustion conditions. The formation of magnesium sulphate, which is molten and sticky at 2050 F. should be minimized, particularly when gas tempertaures at the furnace exit are above 2100 F.; this is accomplished by increasing the aluminum active ingredient in the additive. Second, the magnesia-alumina reaction product reduces the tendency of unreacted but superfine magnesia particles to agglomerate. This control over agglomeration is probably due to the presence of uniformly distributed spinel particles that form cubic crystals of octahedral shape.
Porosity measurements on deposit samples also re vealed that high porosity and large voids were specific to partially dehydrated hydroxides of magnesium and aluminum having particle sizes ranging from 1 to 7 microns. Control of particle size is important because theoretical studies showed that particles larger than microns tend to form undesirably, densely impacted deposits. On the other hand, particles less than 0.5 micron tend to form undesirable cohesive deposits having small voids.
The additive of the present invention is thus suitable for controlling slag deposits on boiler surfaces over a wide range of gas temperatures. Furthermore, by preventing slag formation on tube surfaces, high temperature oil ash corrosion becomes impossible so that tube temperatures may be safely maintained at 1100 F.
To supplement the laboratory research, two power utility companies conducted field trials with additive formulations developed in accordance with the invention. In both cases, the boilers involved were rated at 360,000 lb./hr. of steam at 900 p.s.i.g. and 900 F.
Previously, these boilers were plagued with expensive maintenance and repair costs due to slagging and blocking of superheater elements every 4 to 6 weeks. Several proprietary anti-slagging additives had been tried during a fouryear period but all were expensive and ineffective.
The additive employed in the trials as described in this application was used at a dosage rate of 1 gallon of additive per 1500 gallons of fuel oil, and had the following specific formula and characteristic,
Magnesium:a1uminum--element wt. ratio 10:1 Particle size range, ,a 1-7 Specific gravity at 70 F. 1.35 Flash point, (PM), F. 150' Pour point, F 1O After four weeks of operation with this additive formulation (a) the hard, bonded slag build-up was replaced with a soft, friable powder that was easily removed by soot blowing, (b) bridging in the convection pass of the generating bank was eliminated, and (c) a light coating of additive oxides on the furnace walls was credited with raising superheat temperatures to design conditions for the first time.
A shipboard trial has also been made with an additive as described above but with a magnesiumzaluminum ratio of about 1:1.
The ships boilers being used for this trial suffered from severe superheated slagging because of their stringent design conditions. Typical boiler operating data are:
Solids content, percent by weight (a) 2500 F. gas temperature at the superheater,
(b) 975 F. superheater tube temperature, and
(c) 500 p.s.i.g. steam pressure from 5% to 125% of rated steam flow.
Additive formulation, Additive dosage Furnace Exit temp, F. mgJAl ratio rate gaL/gal.
1,850 or less 10:1 1:1800 1,850-2,150 5:1 1:1500 2150-2350. 3 :1 1 :1200 2,450 or over 1:1 1:100!) Control of low temperature deposits and corrosion Laboratory combustion rig experiments have been conducted with the following formulation:
These experiments have demonstrated that the fuel-oil additive invention reduced sulphuric acid corrosion on low-temperature boiler surfaces by 35% to 66% depending on the additive dosage rate. Laboratory studies have also indicated that a thin, uniform layer of active ingredients deposits on cold end surfaces by a process of agglomeration where they soak up and react with any condensed acid. The residue, after reaction with acid, consists mostly of water-soluble, non-toxic hydrated magnesium and aluminum sulphates that are easily removed by brushing or water-washing.
In related laboratory research experiments, it has been established that time-temperature conditions in industrial flames are not severe enough to dehydrate the active ingredients completely. Furthermore, partial rehydration between the active ingredients and water vapour in the flue gases occurs in the low-temperature region of the boiler. This rehydration phenomenon, by replacing evaporated hydroxyl groups, enhances the chemically basic properties of the magnesium active ingredient and ensures that the aluminum active ingredient will react with acid. The use of completely dehydrated aluminum oxide either amorphous or crystalline is avoided because chemical rehydration and acid neutralization reactions do not occur.
Field trails have also been conducted, using the following formulation:
Magnesium:aluminumelement wt. ratio 10:1 Particle size range, 1. 1-7 Specific gravity at 70 F. 1.35 Flash point (PM), F. 150 Pour point, F. -10
These trials were conducted in a number of power utility boilers that expeirenced serious cold end fouling and corrosion problems. In all trials the additive was initially applied to the rate of 1 gallon per 1500 gallons of fuel oil, after which the dosage rate was gradually reduced to l in 1800.
At the end of 8 weeks operation with additive-treated oil, the draft loss across the airheater of each boiled was unchanged; this indicated that frequent and periodic plugging of the tubular airheaters was no longer a problem. Inspection of the airheaters revealed that the active additive ingredients had completely dried up the original gummy, corrosive cold end deposits and that the thin coating of additive material on the tube surface was loose and powdery.
The boilers, which are now operating regularly on additive treated fuel oil, no longer require soot-blowing in the airheater Zone and regular bi-monthly boiler outages for cleaning and replacement of airheater elements have been eliminated. The extremely low rate of increase in draft loss across the airheaters of these boilers indicates that cleaning of fireside surfaces can be programmed to coincide with annual boiler maintenance.
In one field trial an additive formulation containing a magnesium to aluminum ratio of 10 to 1 resulted in a 90% reduction of in the stack gases when applied at the rate of 1 gallon per 1800 gallons of fuel oil. During this trial, S0 levels were reduced from 30 p.p.m. to 3 p.p.m. and the white acid plume from the stack was eliminated.
Solids content, percent by wt 7 Abatement of acid smut emission 7 Another benefit from using the fuel-oil additive invention has been the abatement of acid smut emission. Without using the additive, acid smut, or soot soaked with sulphuric acid normally builds up in the cold end of a boiler or process and on the stack lining to some equilibrium thickness, after which it suddenly breaks free. Following emission to atmosphere these corrosive, sticky flakes of acid smut fall on people and property creating a seriousnuisance problem and, in some cases, considerable damage to fabrics, crops and automobile finishes.
In large oil-fired boilers, exit gas temperatures often fall below the acid dewpoint. When this occurs and the additive is not used, electrostatic precipitators must be bypassed because of the potential fire hazard from the wet, combustible acid smut that is usually present. In such cases, smut emission is particularly bad, atmospheric pollution ordinances are frequently violated, and many complaints are commonplace.
This problem Was eliminated entirely in one power utility boiler by applying the additive formulation containing an elemental magnesium to aluminum ratio of 10 to 1 at the rate of 1 gallon per 1500 gallons of fuel oil. Furthermore, the electrical resistivity of the solid residues leaving the boiler was improved to the extent that particulate matter can now be collected by the electrostatic precipitators. This solid residue, being dry and powdery, is also easily removed from boiler and dust collector hoppers.
In another power utility boiler the additive formulation containing an elemental magnesium to aluminum ratio of 10:1 was applied at the rate of 1 gallon per 1500 gallons of fuel oil for the purpose of controlling acid smut pollution low temperature corrosion. Reports on the results of this trial state: The effect of the chemicals use are visible, both from a distance and at the station themselves. Most days the air above the stacks is free of what used to be the normal dark plume, and the area around the stations is practically free of fly ash fall-out Even more important to the generating station operators, the soot and slag no longer clog up the huge airheaters connected to the furnaces. Normally, those units, which heat the air thats used in the boiler for combustion purposes, had to be washed out every six weeks The fuel-oil additive described herein provides an economic means of controlling or eliminating boiler operational problems due to incombustible constituents in residual fuel oil. Economic benefits from using the additive include increased boiler availability and efliciency, reduced maintenance and fuel costs, and, in some cases, a financial credit on the sale of vanadium-rich ash collected in boiler and dust collector hoppers. Another major, but less tangible benefit, is the favourable public image created by minimizing the emission of noxious atmospheric pollutants.
The additive, which is normally metered continuously and automatically into the oil supply to each burner, can
be formulated to the specific requirements of a particular boiler. Additive dosage rates will vary according to fuel analysis and combustion conditions, but usually 1 gallon per 1500 gallons of fuel oil is sufficient to control most problems at the cold end of a boiler or the like.
We claim:
1. A fuel oil additive which comprises a dispersion of finely divided particles of partially dehydrated hydroxides of magnesium and aluminum in a petroleum oil containing an anionic or non-ionic surfactant, the weight ratio of magnesiumzaluminum being at least 1:1, said hydroxides having a minimum bound water content of about 0.5% by weight and a maximum bound water content of about 15% by weight.
2. A fuel oil additive as defined in claim 1, said particles being 1 to 7 microns in size and the solids content of said dispersion being about 40 to 60% by weight.
3. A fuel oil additive as defined in claim 1, said dispersion having a maximum Saybolt viscosity of 115 universal seconds at 80 F.
4. A fuel oil additive as defined in claim 1, the elemental magnesium in said dispersion being greater than the amount of the elemental aluminum in said dispersion.
5. A fuel oil additive as defined in claim 1, said petro' leurn oil having a maximum Saybolt viscosity of 35 universal seconds at 100 F.
6. A fuel oil additive as defined in claim 1, said surfactant being present in the proportion of 0.7 to 3.5%
by weight.
7. A fuel oil additive as defined in claim 1, said surfactant being selected from the group consisting of glycerol stearates and laurates, lecithin, fatty acids, and heavy metal soaps of stearic, naphthenic and rosin acids.
8. A fuel oil additive as defined in claim 1, said particles having a specific surface area of 400 to 1400 square meters per gram.
9. A fuel oil additive as defined in claim 1, said particles being porous, the diameter of each pore in said particles being in the range of at least 17 angstrom units.
10. A fuel oil additive as defined in claim 1, said particles being porous, the diameter of each pore in said particles being in the range of 17 to 2 0 angstrom units.
11. A fuel oil additive as defined in claim 1, said particles having about 0.5 to 5% by weight of bound water.
12. A fuel oil additive as defined in claim 1, the weight ratio of elemental magnesiumzaluminum being about 10:1.
13. A method of preventing oil ash slagging, low temperature corrosion, acid smut emission, of reducing the level of S0 and nitrogen oxides in flue gases, chemically neutralizing and drying up gummy, corrosive deposits that form below acid dewpoint temperatures, in oil fired boilers comprising operating said boilers on a fuel oil containing about 1 gallon of additive in 1000 gallons of fuel oil to 1 gallon of additive in 2000 gallons of fuel oil, an additive comprising a petroleum oil having dispersed therein in the presence of an anionic or non-ionic surfactant 40 to 60% by weight of 1 to 7 micron particles of partially dehydrated hydroxides of Mg and Al having a minimum bound water content of about 0.5% by weight and a maximum bound water content of about 15% by weight, the weight ratio of magnesium:aluminum being at least 1:1.
References Cited UNITED STATES PATENTS 2,845,338 7/1958 Ryznar et a1 4467 X 2,949,008 8/1960 Rocchini et al. 4468 X 3,018,172 1/1962 Tillman 4451 3,067,018 12/ 1962 Voorhees 4451 3,078,662 2/ 1963 Rocchini et al. 4468 X DANIEL E. WYMAN, Primary Examiner W. J. SHINE, Assistant Examiner
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US77879968A | 1968-11-25 | 1968-11-25 |
Publications (1)
Publication Number | Publication Date |
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US3514273A true US3514273A (en) | 1970-05-26 |
Family
ID=25114414
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US778799A Expired - Lifetime US3514273A (en) | 1968-11-25 | 1968-11-25 | Fuel oil additive |
Country Status (1)
Country | Link |
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US (1) | US3514273A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4006591A (en) * | 1975-08-11 | 1977-02-08 | Faith Industries, Inc. | Jet reaction turbine with rotating combustor for burning slurry fuels |
US4340493A (en) * | 1980-03-14 | 1982-07-20 | Kyowa Chemical Industry Co. Ltd. | Detergent-dispersant composition for lubricating or fuel oils |
US4530701A (en) * | 1982-05-17 | 1985-07-23 | Nalco Chemical Company | Process of manufacturing a co-fuel additive with combustion-modifying effects |
US4783197A (en) * | 1983-07-14 | 1988-11-08 | Ab Carbogel | Composition and a method of capturing sulphur |
US4832701A (en) * | 1986-06-17 | 1989-05-23 | Intevep, S.A. | Process for the regeneration of an additive used to control emissions during the combustion of high sulfur fuel |
US4886519A (en) * | 1983-11-02 | 1989-12-12 | Petroleum Fermentations N.V. | Method for reducing sox emissions during the combustion of sulfur-containing combustible compositions |
WO1991004310A1 (en) * | 1989-09-20 | 1991-04-04 | Petroferm Inc. | Method for reducing sox emissions during the combustion of sulfur-containing combustible compositions |
USRE36983E (en) * | 1983-11-02 | 2000-12-12 | Petroferm Inc. | Pre-atomized fuels and process for producing same |
US9994492B2 (en) | 2013-02-20 | 2018-06-12 | Yara Uk Limited | Fertiliser coating containing micronutrients |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2845338A (en) * | 1953-10-15 | 1958-07-29 | Nat Aluminate Corp | Fuel additive for removing and inhibiting fireside deposits |
US2949008A (en) * | 1958-01-29 | 1960-08-16 | Gulf Research Development Co | Residual fuels |
US3018172A (en) * | 1957-05-13 | 1962-01-23 | Continental Oil Co | Aluminum-containing additive for fuel oil compositions and method of preparing the same |
US3067018A (en) * | 1957-10-29 | 1962-12-04 | Bray Oil Co | Colloidal additives for fuel oils |
US3078662A (en) * | 1959-02-24 | 1963-02-26 | Gulf Research Development Co | Non-corrosive vanadiumcontaining fuels |
-
1968
- 1968-11-25 US US778799A patent/US3514273A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2845338A (en) * | 1953-10-15 | 1958-07-29 | Nat Aluminate Corp | Fuel additive for removing and inhibiting fireside deposits |
US3018172A (en) * | 1957-05-13 | 1962-01-23 | Continental Oil Co | Aluminum-containing additive for fuel oil compositions and method of preparing the same |
US3067018A (en) * | 1957-10-29 | 1962-12-04 | Bray Oil Co | Colloidal additives for fuel oils |
US2949008A (en) * | 1958-01-29 | 1960-08-16 | Gulf Research Development Co | Residual fuels |
US3078662A (en) * | 1959-02-24 | 1963-02-26 | Gulf Research Development Co | Non-corrosive vanadiumcontaining fuels |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4006591A (en) * | 1975-08-11 | 1977-02-08 | Faith Industries, Inc. | Jet reaction turbine with rotating combustor for burning slurry fuels |
US4340493A (en) * | 1980-03-14 | 1982-07-20 | Kyowa Chemical Industry Co. Ltd. | Detergent-dispersant composition for lubricating or fuel oils |
US4530701A (en) * | 1982-05-17 | 1985-07-23 | Nalco Chemical Company | Process of manufacturing a co-fuel additive with combustion-modifying effects |
US4783197A (en) * | 1983-07-14 | 1988-11-08 | Ab Carbogel | Composition and a method of capturing sulphur |
US4886519A (en) * | 1983-11-02 | 1989-12-12 | Petroleum Fermentations N.V. | Method for reducing sox emissions during the combustion of sulfur-containing combustible compositions |
USRE36983E (en) * | 1983-11-02 | 2000-12-12 | Petroferm Inc. | Pre-atomized fuels and process for producing same |
US4832701A (en) * | 1986-06-17 | 1989-05-23 | Intevep, S.A. | Process for the regeneration of an additive used to control emissions during the combustion of high sulfur fuel |
WO1991004310A1 (en) * | 1989-09-20 | 1991-04-04 | Petroferm Inc. | Method for reducing sox emissions during the combustion of sulfur-containing combustible compositions |
JPH05501889A (en) * | 1989-09-20 | 1993-04-08 | インテヴェップ,エス.エイ. | Method for suppressing the release of oxidized sulfur compounds during combustion of sulfur-containing combustible compositions |
US9994492B2 (en) | 2013-02-20 | 2018-06-12 | Yara Uk Limited | Fertiliser coating containing micronutrients |
US10118867B2 (en) | 2013-02-20 | 2018-11-06 | Yara Uk Limited | Fertiliser coating containing micronutrients |
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