US20200172817A1 - Use of peroxyacids/hydrogen peroxide for removal of metal components from petroleum and hydrocarbon streams for downstream applications - Google Patents
Use of peroxyacids/hydrogen peroxide for removal of metal components from petroleum and hydrocarbon streams for downstream applications Download PDFInfo
- Publication number
- US20200172817A1 US20200172817A1 US16/701,684 US201916701684A US2020172817A1 US 20200172817 A1 US20200172817 A1 US 20200172817A1 US 201916701684 A US201916701684 A US 201916701684A US 2020172817 A1 US2020172817 A1 US 2020172817A1
- Authority
- US
- United States
- Prior art keywords
- ppm
- water
- peroxyacid
- oil
- emulsion
- 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.)
- Abandoned
Links
- 150000004965 peroxy acids Chemical class 0.000 title claims abstract description 118
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 91
- 239000002184 metal Substances 0.000 title claims abstract description 91
- 239000003208 petroleum Substances 0.000 title claims abstract description 50
- 229930195733 hydrocarbon Natural products 0.000 title claims description 83
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 83
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 64
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims description 33
- 238000000034 method Methods 0.000 claims abstract description 113
- 239000000203 mixture Substances 0.000 claims abstract description 67
- 239000003921 oil Substances 0.000 claims abstract description 67
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 161
- 229910001868 water Inorganic materials 0.000 claims description 154
- 239000000839 emulsion Substances 0.000 claims description 91
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 58
- 239000010779 crude oil Substances 0.000 claims description 53
- 150000002739 metals Chemical class 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 36
- 229910052742 iron Inorganic materials 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 23
- 238000011033 desalting Methods 0.000 claims description 20
- 239000003209 petroleum derivative Substances 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 238000005260 corrosion Methods 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 13
- 239000013522 chelant Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000011575 calcium Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 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 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000002455 scale inhibitor Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000000080 wetting agent Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 125000002524 organometallic group Chemical group 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 150000003017 phosphorus Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 150000004763 sulfides Chemical class 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 18
- 239000007787 solid Substances 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000000356 contaminant Substances 0.000 abstract description 9
- 230000000116 mitigating effect Effects 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 7
- 239000000571 coke Substances 0.000 abstract description 5
- 230000002708 enhancing effect Effects 0.000 abstract description 5
- 241000894006 Bacteria Species 0.000 abstract description 4
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 238000011143 downstream manufacturing Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000002516 radical scavenger Substances 0.000 abstract description 2
- 150000003751 zinc Chemical class 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 64
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 38
- 230000008569 process Effects 0.000 description 25
- -1 oxalic acid Chemical class 0.000 description 22
- 239000000523 sample Substances 0.000 description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000007800 oxidant agent Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 230000008901 benefit Effects 0.000 description 13
- 150000001735 carboxylic acids Chemical class 0.000 description 13
- 238000009616 inductively coupled plasma Methods 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000176 sodium gluconate Substances 0.000 description 11
- 235000012207 sodium gluconate Nutrition 0.000 description 11
- 229940005574 sodium gluconate Drugs 0.000 description 11
- 238000009472 formulation Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 7
- 230000005684 electric field Effects 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 235000011054 acetic acid Nutrition 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 4
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000005083 Zinc sulfide Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 239000003139 biocide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 150000004966 inorganic peroxy acids Chemical class 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000004967 organic peroxy acids Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 150000004978 peroxycarbonates Chemical class 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229960001922 sodium perborate Drugs 0.000 description 2
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 2
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- 239000004343 Calcium peroxide Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- 239000002007 Fuel grade coke Substances 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical compound [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 208000002430 Multiple chemical sensitivity Diseases 0.000 description 1
- 208000034809 Product contamination Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000012062 aqueous buffer Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 239000002551 biofuel Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- LHJQIRIGXXHNLA-UHFFFAOYSA-N calcium peroxide Chemical compound [Ca+2].[O-][O-] LHJQIRIGXXHNLA-UHFFFAOYSA-N 0.000 description 1
- 235000019402 calcium peroxide Nutrition 0.000 description 1
- LKVLGPGMWVYUQI-UHFFFAOYSA-L calcium;naphthalene-2-carboxylate Chemical class [Ca+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 LKVLGPGMWVYUQI-UHFFFAOYSA-L 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 229940060367 inert ingredients Drugs 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- GNVXPFBEZCSHQZ-UHFFFAOYSA-N iron(2+);sulfide Chemical compound [S-2].[Fe+2] GNVXPFBEZCSHQZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- 229960004995 magnesium peroxide Drugs 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000012354 overpressurization Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- CMFNMSMUKZHDEY-UHFFFAOYSA-N peroxynitrous acid Chemical compound OON=O CMFNMSMUKZHDEY-UHFFFAOYSA-N 0.000 description 1
- 150000004971 peroxyphosphoric acids Chemical class 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000003362 replicative effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UHCGLDSRFKGERO-UHFFFAOYSA-N strontium peroxide Chemical compound [Sr+2].[O-][O-] UHCGLDSRFKGERO-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WBGSMIRITKHZNA-UHFFFAOYSA-M trisodium;dioxido(oxidooxy)borane Chemical compound [Na+].[Na+].[Na+].[O-]OB([O-])[O-] WBGSMIRITKHZNA-UHFFFAOYSA-M 0.000 description 1
- HOOCZFRHVPMDTH-UHFFFAOYSA-M trisodium;dioxido(oxidooxy)borane;tetrahydrate Chemical compound O.O.O.O.[Na+].[Na+].[Na+].[O-]OB([O-])[O-] HOOCZFRHVPMDTH-UHFFFAOYSA-M 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical class OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000004457 water analysis Methods 0.000 description 1
- 239000008215 water for injection Substances 0.000 description 1
- 229940105296 zinc peroxide Drugs 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/02—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by electric or magnetic means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
Definitions
- the disclosure relates to the use of peroxyacid formulations, including but not limited to peracetic acid and performic acid, for enhancement of downstream processes through removal of soluble and particulate metal complexes from petroleum oils and refinery feedstocks and/or streams. This serves to minimize fouling, decrease the propensity for a solid stabilized emulsion and in turn, improve waste water quality.
- the methods and compositions are particularly useful for mitigation of heavy metals in petroleum oil and for offsetting potential solid loading resulting from use of a metal based H 2 S scavenger or other commonly applied metal-based additives.
- the methods and compositions are also useful for enhancing coke quality via decreased metal concentrations, reducing bacteria in slop oil and crude tanks, as well as reducing downstream catalyst poisoning.
- an enhanced solids removal agent or demulsifier that can promote partitioning of inorganic particulate, such as iron sulfide, from an emulsion phase to a water phase. This is essential to increase the lifetime of process equipment downstream of the desalter in a refinery, to ensure compliance with environmental regulations in streams processed by refinery waste water treatment plants and to enhance profitability.
- U.S. Pat. Nos. 4,778,589 and 4,789,463 disclose the use of hydroxycarboxylic acids as chemical aids for metals removal in refinery desalting processes.
- U.S. Pat. No. 4,833,109 to Reynolds discloses the use of dibasic carboxylic acids, particularly oxalic acid, for the removal of divalent metals, including calcium and iron. Wash water addition of hydroxyacids for removing metals during desalting processes is taught in U.S. Pat. Nos. 7,497,943, 4,778,589 and 4,789,463.
- U.S. Pat. Nos. 5,114,566 and 4,992,210 teach the removal of corrosive contaminants from crude oil by adding a composition including certain organic amines having a pKb from 2 to 6 and potassium hydroxide to the desalter wash water. The composition is stated to effectively remove chlorides from the crude oil at the desalter.
- U.S. Pat. No. 5,078,858 suggests the addition of an oxalic or citric acid chelant to the desalter wash water.
- U.S. Pat. No. 5,256,304 is directed to the addition of a polymeric tannin material to oily waste water to demulsify oil and flocculate metal ions.
- U.S. Pat. No. 5,080,779 teaches the use of a chelant in a two stage desalter process for the removal of iron. Other methods involve the use of increased concentrations of emulsion breakers (aka demulsifiers).
- Peroxyacids particularly peracetic acid
- U.S. Pat. No 9,242,879 discloses their use for treatment of drilling fluids, frac fluids, flowback water and disposal water.
- Application of peroxyacids in the area of commercial well drilling operations have been limited to use as biocides in aqueous systems.
- use of peracetic acid has a small environmental footprint, due in part to its decomposition into innocuous components (i.e., acetic acid, oxygen, carbon dioxide and water).
- a further objective of the invention is to develop methods for solids stabilized emulsion control.
- a disclosure on a mechanism to prevent this phenomenon Minimizing the concentration of particulate content in crude oil should ultimately facilitate better salt removal and dehydrating efficiency during emulsion resolution processes. Therefore, the peroxyacid formulations can also be considered emulsion breakers in their own right.
- a further objective of the invention is to develop methods for removal of organometallic complexes such as porphyrinic iron, nickel or vanadium or calcium naphthenates. These organometallic compounds are not readily removed by normal desalting practices and can cause coker furnace fouling, finished products outside of specification and deactivation of hydroprocessing catalysts.
- the present disclosure is related to the use of peroxyacids compositions and methods of employing peroxyacids for removal of metals and particulate contained in petroleum oil, crude oil, slop oil, and other hydrocarbon streams in various refinery applications.
- the use of peroxyacid compositions and methods of employing them in various petroleum oil and refinery streams overcomes a significant need in the art for improved methods for removing particulate iron sulfide and zinc sulfide, along with other contaminants.
- a method for removing particulates in petroleum oil and/or hydrocarbon feedstocks includes the steps of: mixing petroleum oil and/or hydrocarbon feedstock with water to form an emulsion comprising a hydrocarbon phase and a water phase; adding a peroxyacid composition to the emulsion, wherein the peroxyacid causes the particulates to move from the hydrocarbon phase into the water phase; and separating the hydrocarbon phase from the water phase to remove the particulates and the peroxyacid composition from the emulsion.
- the peroxyacid oxidizes and chelates the particulates in the emulsion, and wherein the particulates are soluble and particulate metal complexes.
- the peroxyacid composition comprises a C1-C22 peroxyacid, a C1-C22 carboxylic acid, and hydrogen peroxide.
- the peroxyacid is at least one of peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic, peroxyascorbic, peroxyhydroxyacetic, peroxyoxalic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric acid.
- At least 100 ppm of the peroxyacid is added to the emulsion, or up to about 10,000 ppm of the peroxyacid is added to the emulsion.
- at least one additional agent that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents is added to the emulsion with the peroxyacid composition.
- the mixture of petroleum oil and/or hydrocarbon feedstock in water is resolved in an electrostatic desalting unit.
- the methods further include adding an effective amount of an emulsion breaker or demulsifier to aid in the separation of the oil from the water phase containing the particulates.
- the methods further include settling the petroleum oil and/or hydrocarbon feedstock in a tank to enable the water, peroxyacid composition and particulates to settle on the bottom thereof from the petroleum oil and/or hydrocarbon feedstock.
- the petroleum oil and/or hydrocarbon feedstock is a produced crude oil and is obtained from a pipeline that directs a flow of produced crude oil.
- the petroleum oil and/or hydrocarbon feedstock once separated from the water phase does not contain any peroxyacid composition.
- the petroleum oil and/or hydrocarbon feedstock comprise petroleum oil, crude oil, slop oil, and other hydrocarbon streams from a refinery application.
- the method can exclude the use of phosphoric or phosphorus acids.
- a crude oil emulsion treatment consists of: crude oil; a peroxyacid composition for transferring metals and particulates from a hydrocarbon phase to a water phase; and a source of water.
- the treated crude oil emulsion further comprises at least one additional component that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents.
- an emulsion treatment consists of: petroleum oil, crude oil, slop oil, or another hydrocarbon stream in a refinery application; a peroxyacid composition for transferring metals and particulates from a hydrocarbon phase to a water phase; and a source of water.
- the treated emulsion further comprises at least one additional component that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents.
- FIG. 1 shows a general diagram of a desalting process.
- FIG. 2 shows a graph of iron removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 3 shows a graph of nickel removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 4 shows a graph of zinc removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 5 shows a graph of iron removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 6 shows a graph of zinc removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases.
- FIG. 7 is a graph showing iron removal in a resolved water phase by various peroxycarboxylic and carboxylic acids.
- FIG. 8 is a graph showing nickel and zinc removal in a resolved water phase by various chemistries.
- FIG. 9 is a graph showing the amount (ppm) of filterable solids that remained on the top oil fraction after emulsion resolution using various chemistries.
- FIG. 10 is a color photograph of four samples after centrifugation showing the resulting resolved emulsions of EC2111A and EC6779A samples at 1000 ppm and 5000 ppm.
- the present invention relates to the methods and application of peroxyacid compositions for particulate and metal removal for improving or enhancing downstream processes for petroleum oil and refinery hydrocarbon feedstocks and streams.
- the methods of using peroxyacid compositions have many advantages over conventional demetallization technologies. For example, the methods can take place before, after or simultaneous with a desalting step. The effective removal of metals and particulates before a desalting process can significantly minimize the effects of these contaminants on the crude unit and further downstream operations. Having metals and particulates removed before a desalting step then promotes more efficient desalting as well. Benefits can include reduced crude unit corrosion, crude system fouling, energy costs and desalting process demarks, and finished product contamination.
- description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example, 1.2, 3.8, 11 ⁇ 2, and 43 ⁇ 4. This applies regardless of the breadth of the range.
- the term “about,” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable, including, but not limited to, mass, volume, time, distance, wave length, frequency, voltage, current, and electromagnetic field. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods and the like.
- the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. The term “about” also encompasses these variations. Whether or not modified by the term “about,” the claims include equivalents to the quantities.
- compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein.
- “consisting essentially of” means that the methods, systems, apparatuses and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, apparatuses, and compositions.
- actives or “percent actives” or “percent by weight actives” or “actives concentration” are used interchangeably herein and refers to the concentration of those ingredients involved expressed as a percentage minus inert ingredients such as water or salts.
- the terms “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.
- waters includes water in industrial and/or energy service applications.
- Waters in industrial and/or energy service applications include for example: aquifer water, river water, sea water, produced water, fresh water, water for injection, secondary flooding water, hot water or feedwater, ethanol/bio-fuels process waters, pretreatment and utility waters, membrane system liquids, ion-exchange bed liquids, water used in the process/manufacture of paper, ceiling tiles, fiber board, microelectronics, E-coat liquids, electrodeposition liquids, process cleaning liquids, oil exploration services liquids, oil well completion fluids, oil well workover fluids, drilling additive fluids, oil fracturing fluids, oil and gas wells, flowline water systems, natural gas water systems, or the like.
- weight percent refers to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100.
- peroxyacids and peroxyacid compositions are able to increase the hydrophilicity of particulate materials (including soluble and particulate metal complexes) in petroleum oil and refinery streams to enhance their removal from the oil/water emulsions.
- the approximate amount of peroxyacid required to achieve the desired amount of metal or particulate removal from an oil stream can be determined by one skilled in the art by taking into account characteristics of the stream being treated.
- the concentration of peroxyacid sufficient to demetallize a petroleum oil or refinery stream can range from 1 ppm to 10,000 ppm, between about 1,000 ppm and about 5,000 ppm, or ranges there between.
- the concentration of peroxyacid sufficient to demetallize a petroleum oil or refinery stream can be at least about 100 ppm, at least about 1,000 ppm, at least about 2,000 ppm, at least about 3,000 ppm, at least about 4,000 ppm, at least about 5,000 ppm, at least about 6,000 ppm, at least about 7,000 ppm, at least about 8,000 ppm, at least about 9,000 ppm, at least about 10,000 ppm, or ranges there between.
- Suitable peroxyacids include both organic and inorganic peroxyacids as set forth herein.
- Organic peroxyacids include for example peroxycarboxylic acids that generally have the formula RCO 3 H, where, for example, R is defined as an alkyl, alkenyl, alkyne, acyclic, alicyclic group, aryl, arylalkyl, cycloalkyl, aromatic, heteroaryl, heterocyclic group, or hydrogen.
- R-group can be saturated or unsaturated as well as substituted or unsubstituted.
- Peroxyacids can be made, for example, by the direct action of an oxidizing agent on a carboxylic acid, by auto-oxidation of aldehydes, or from acid chlorides, and hydrides, or carboxylic anhydrides with hydrogen or sodium peroxide. Any suitable C 1 -C 26 peroxyacid, such as a peroxycarboxylic acid can be used.
- the C 1 -C 26 percarboxylic acid is a C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , C 25 , and/or C 26 percarboxylic acid.
- a C 1 -C 22 peroxyacid is preferred, or combinations thereof.
- Peroxyacids may include short chain and/or medium chain peroxyacids.
- a “short chain peracid” refers to a peroxyacid having a carbon chain between 1 and 4 carbons. Short chain peracids have the benefit of often being highly miscible in water at 25° C. Examples of short chain carboxylic acids include formic acid, acetic acid, propionic acid, and butyric acid.
- Peroxyacetic (or peracetic) acid is a peroxyacid having the formula: CH 3 COOOH.
- peroxyacetic acid is a liquid having an acrid odor at higher concentrations and is freely soluble in water, alcohol, ether, and sulfuric acid.
- Peroxyacetic acid can be prepared through any number of methods known to those of skill in the art including preparation from acetaldehyde and oxygen in the presence of cobalt acetate.
- a solution of peroxyacetic acid can be obtained by combining acetic acid with hydrogen peroxide.
- the compositions of the invention employ a C1 to C4 peroxyacid.
- the phrase “medium chain peracid” refers to a peroxyacid having a carbon chain between 5 and 22 carbons in length.
- the phrase “medium chain carboxylic acid” can refer to a carboxylic acid that has a critical micellization concentration greater than 1 mM in aqueous buffers at neutral pH. It is also common for medium chain carboxylic acids to have an unpleasant odor.
- Medium chain carboxylic acids exclude carboxylic acids that are infinitely soluble or miscible with water at 20° C.
- Medium chain carboxylic acids include carboxylic acids with boiling points (at 760 mm Hg pressure) of 180 to 300° C.
- medium chain carboxylic acids include carboxylic acids with boiling points (at 760 mm Hg pressure) of 200 to 300° C. In an embodiment, 20 medium chain carboxylic acids include those with solubility in water of less than 1 g/L at 25° C. Examples of medium chain carboxylic acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and dodecanoic acid.
- Peroxyacids useful in the methods described herein include meta-chloroperoxybenzoic, peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic, peroxyascorbic, peroxyhydroxyacetic, peroxyoxalic, meta-chloroperoxybenzoic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric acid and mixtures thereof.
- Inorganic peroxyacids such as peroxymonosulfuric acid (Caro's acid) are not excluded from the peroxyacid and/or peroxyacid composition
- the composition includes one or more C1 to C4 peroxyacids and one or more C5 to C22 peroxyacids.
- the ratio of short chain peroxyacid to medium chain peroxyacid can be about 1:1 to about 10:1.
- a peroxyacid composition also includes an organic acid (i.e. corresponding carboxylic acid) and an oxidizing agent.
- the peroxyacid composition can be formed by an organic acid and an oxidizing agent.
- the compositions can be pre-formed.
- peroxyacid compositions may be generated in situ. Additional description of exemplary in situ methods for peroxyacids is provided for example in U.S. Pat. Nos. 9,845,290, 9,518,013, 8,846,107 and 8,877,254, which are herein incorporated by reference in its entirety.
- the peroxyacid compositions may also include an oxidizing agent.
- the oxidizing agent is hydrogen peroxide.
- Hydrogen peroxide, H 2 O 2 provides the advantages of having a high ratio of active oxygen because of its low molecular weight (34.014 g/mole) and by being compatible with numerous substances that can be treated by methods of the invention because it is a weakly acidic, clear, and colorless liquid.
- Another advantage of hydrogen peroxide is that it decomposes into innocuous water and oxygen.
- the peroxyacid compositions can include any desired ratio of hydrogen peroxide.
- the hydrogen peroxide in the percarboxylic acid composition has a concentration from about 0.5 wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 10 wt-%. In other embodiments, the hydrogen peroxide has a concentration from about 1 wt-% to about 2 wt-%.
- the hydrogen peroxide has a concentration at about 0.5 wt-%, 1 wt-%, 2 wt-%, 3 wt-%, 4 wt-%, 5 wt-%, 6 wt-%, 7 wt-%, 8 wt-%, 9 wt-%, or 10 wt-%.
- the hydrogen peroxide has a concentration at about 1 wt-%, 1.1 wt-%, 1.2 wt-%, 1.3 wt-%, 1.4 wt-%, 1.5 wt-%, 1.6 wt-%, 1.7 wt-%, 1.8 wt-%, 1.9 wt-%, 2 wt-%, 2.1 wt-%, 2.2 wt-%, 2.3 wt-%, 2.4 wt-%, 2.5 wt-%, 2.6 wt-%, 2.7 wt-%, 2.8 wt-%, 2.9 wt-%, 3 wt-%, 3.1 wt-%, 3.2 wt-%, 3.3 wt-%, 3.4 wt-%, 3.5 wt-%, 3.6 wt-%, 3.7 wt-%, 3.8 wt-%, 3.9 wt-%, or 4
- Additional oxidizing agents include for example, the following types of compounds or sources of these compounds, or alkali metal salts including these types of compounds, or forming an adduct therewith: hydrogen peroxide, urea-hydrogen peroxide complexes or hydrogen peroxide donors of: group 1 (IA) oxidizing agents, for example lithium peroxide, sodium peroxide; group 2 (IIA) oxidizing agents, for example magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide; group 12 (IIB) oxidizing agents, for example zinc peroxide; group 13 (IIIA) oxidizing agents, for example boron compounds, such as perborates, for example sodium perborate hexahydrate of the formula Na 2 [B 2 (O 2 ) 2 (OH) 4 ] ⁇ 6H 2 O (also called sodium perborate tetrahydrate); sodium peroxyborate tetrahydrate of the formula Na 2 B 2 (O 2 ) 2 [(OH) 4 ] ⁇ 4H
- peroxyacids or peroxyacid compositions
- the feedstocks include any hydrocarbon feedstock including for example crude oil, slop oil, heavy residua, atmospheric or vacuum residua, deasphalted oils derived from the crude oil or residua, shale oil, liquified coal and tar sand effluent, and the like and blends thereof.
- removing the metals and/or particulates from the petroleum oil and feedstocks (namely the hydrocarbon phase) is meant to include any and all partitioning, sequestering, separating, transferring, eliminating, dividing, removing, of one or more metal and/or particulate from the hydrocarbon phase to any extent.
- particulates can include inorganic fines that are naturally occurring in crude oil such as silt, clays, silicates and metal oxides. These inorganic materials may not reactive with the peroxyacids but can be removed indirectly during an emulsion resolution process treated with the additive (vide infra). Particulates can also include alkali metal salts, including but not limited to, calcium carbonate (CaCO 3 ), calcium sulfate (CaSO 4 ), iron oxides (Fe 2 O 3 and Fe 3 O 4 ), and barium sulfate (BaSO 4 ).
- CaCO 3 calcium carbonate
- CaSO 4 calcium sulfate
- Fe 2 O 3 and Fe 3 O 4 iron oxides
- BaSO 4 barium sulfate
- other heavy metals can include, but are not limited to, metal sulfides, metal chlorides, organo-porphyrins or other organometallic complexes that may react with the peroxyacid.
- Metals suitable for removal using the process of this invention include, but are not limited to those of Groups 1, 2, 4, 5, 8, and 10 of the Periodic Table.
- Exemplary metals include iron, zinc, nickel, vanadium, aluminum, magnesium, titanium, sodium, potassium, calcium, and silicon.
- the particulates can also include chloride salts, sulfur, oxides and sulfides.
- Particulates can also include inorganic molecules such as iron sulfide (FeS), zinc sulfide (ZnS) and aluminum chloride (AlCl 3 ) that are naturally occurring or arise from other chemical additives or corrosion processes.
- refinery applications include, but are not limited to raw crude processing, desalting, tankage treatment and dehydration, slop oil resolution and mitigation, FCC desalter performance enhancement, and waste water contaminate removal and processing.
- the methods of employing peroxyacids to remove fine particulates and metals from petroleum oils and refinery feedstocks includes applying or adding a peroxyacid to a wash water source, a petroleum oil and/or hydrocarbon feedstock.
- a peroxyacid includes, but is not limited to, crude oil, slop oil, and water in oil or oil in water emulsions.
- the oil or feedstock to be treated should preferably be in a liquid state at the selected process conditions in order to facilitate contact between the oil and the aqueous extractant (i.e. the peroxyacid and/or water). As one skilled in the art appreciates this may be accomplished by heating the oil or by the addition of a suitable solvent, e.g. a lower boiling hydrocarbon oil, as needed.
- the petroleum oil or feedstock to be treated is delivered to a pipeline with a heat exchanger. In such embodiments, a water supply line connects to the flow of heated oil and is delivered with the oil.
- the methods may comprise, consist of and/or consist essentially of one or more of the following steps: add water and peroxyacid to a petroleum oil or hydrocarbon feedstock; add a peroxyacid to an emulsion of oil (hydrocarbon phase) and water (aqueous/water phase); water-wet particulates; oxidize metals; chelate a metal; separate the water phase containing residual peroxyacid, water soluble metal complexes, and particulates from the hydrocarbon phase.
- the peroxyacid can be added to an emulsion formed of a hydrocarbon phase and a water phase without further addition of water.
- the methods of adding a peroxyacid to the petroleum oil or feedstock may precede a desalting step.
- a refinery's desalting unit is designed to remove entrained water, water-soluble contaminants and oil-insoluble particulates from crude oil.
- Crude oil is defined here as any hydrocarbon stream entering a refinery that will be processed through the desalter. This crucial step of the refining process is necessary to extend the lifetime of process equipment downstream of the unit, render the crude oil less corrosive, protect downstream refinery equipment from fouling, and to maximize throughput.
- the desalter achieves this by (I) providing crude oil; (II) adding wash water to the crude oil and mixing the two phases together to form an emulsion; (III) subsequently breaking the emulsion that is formed to provide an aqueous phase and a hydrocarbon phase containing a lower concentration of salt, particulate and metals.
- the resolved hydrocarbon phase is commonly drawn off the top of the unit and sent to a fractionator tower.
- the water phase containing water-soluble metal salt compounds and sediment is discharged out the bottom of the unit and sent to a waste water treatment plant for processing.
- a general schematic of this process is given in FIG. 1 .
- Desalting is traditionally enhanced by application of a high voltage electric field, heat, and by the addition of chemical additives such as emulsion breakers, solids-removal agents, and coagulants.
- Water soluble salts in crude oil are typically chloride, sulfate or carbonate salts of sodium, magnesium, or calcium. If the salts are not effectively removed to the water phase, scale may result. This will reduce throughput and potentially increase operating costs.
- the salts will hydrolyze to form their acid analog, which will accelerate corrosion rates in the process vessels downstream of the unit and compromise their structural integrity.
- Sediment is largely composed of naturally occurring materials, such as silicas, clays, asphaltenes, and metal oxides, resulting from the geologic formation from which the crude oil was extracted or from corrosion. This material may gravity settle in the desalter if the particle size of the sediment and conditions within the unit (emulsion viscosity, crude oil retention times etc.) are favorable. Effective removal of this water-insoluble material will increase throughput by diminishing fouling rates and will increase profitability for the refiner by decreasing the frequency at which heat exchangers must be cleaned.
- naturally occurring materials such as silicas, clays, asphaltenes, and metal oxides
- Fine particulate also known as suspended solids, are hydrocarbon and water insoluble inorganics that are too small to gravity settle in the desalter. These inorganics are largely introduced into crude oil from the geological formation (sand, silt, alkali metal salts, etc.), from corrosion processes (FeS) or from upstream additives (metal based H 2 S scavengers, aluminum-based coagulants, etc.).
- FCC fluid catalytic cracking
- fine particulate can act as an emulsifier and exacerbate emulsion stability at the desalter, which may lead to a decrease in desalting efficiency and/or an increase in the volume of slop oil generated.
- the crude oil aforementioned and desalter emulsions may have high concentrations of metals, including iron sulfide, and the methods disclosed herein beneficially removes those metals and particulates more efficiently than in a typical desalting operation.
- the peroxyacid formulation may enhance overall desalter performance by promoting increased removal of salt, sediment and fine particulate from the hydrocarbon phase.
- the peroxyacid is provided or introduced (e.g. injected) into a pipe and/or tank upstream of the desalter to contact the hydrocarbon.
- the peroxyacid is preferably injected upstream of a location where the treated feed will have adequate settling time to allow the water and hydrocarbon phases to resolve and the particulates to migrate to the water phase.
- the methods of adding a peroxyacid to the petroleum oil or feedback may be before, simultaneous, or after the addition of wash water to the crude oil.
- the method of adding a peroxyacid may also be directly into a water phase.
- the methods may also include the step of adding an effective amount of at least one additional agent or component that is water or a solvent, a corrosion inhibitor, a demulsifier (such as an oxyalkylate), a scale inhibitor, metal chelants, wetting agents and mixtures thereof.
- the methods may also include the step of adding an effective amount of an emulsion breaker (i.e. demulsifier) to aid in the separation of the oil from the water phase containing the particulates.
- the methods of adding a peroxyacid to the petroleum oil or feedstock may precede a tankage dehydration step. This may relate to dehydration of a hydrocarbon or petroleum oil stream entering a refinery tank farm or static settling of an emulsion downstream of the desalter.
- the contact time for the peroxyacid will vary depending upon the process and wash water, petroleum oil and/or hydrocarbon feedstock to be treated.
- the peroxyacid is simply added and mixed with the oil, and then is removed along with the water phase and particulates.
- the amount of peroxyacid added to the petroleum oil or feedstock will depend upon the oil or feedstock to be treated.
- the amount of metals (e.g. iron) or particulates in the oil or feedstock can vary significantly.
- slop oil may have a higher concentration of metals and particulates than crude oil.
- the concentration of peroxyacid provided is between about 1 ppm and about 50,000 ppm, between about 1,000 ppm and about 30,000 ppm, between about 1,000 ppm and about 20,000 ppm, or ranges there between. In an aspect, the concentration of peroxyacid is at least about 1 ppm, at least about 1,000 ppm, at least about 2,000 ppm, at least about 3,000 ppm, at least about 4,000 ppm, at least about 5,000 ppm, at least about 6,000 ppm, at least about 7,000 ppm, at least about 8,000 ppm, at least about 9,000 ppm, at least about 10,000 ppm, or ranges there between.
- one or more demulsifiers are added to the crude oil or wash water.
- the peroxyacid may also act as a demulsifier.
- the methods beneficially reduce the metals and particulate content in the petroleum oil or refinery stream by at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 99%, or complete removal.
- the percentage of reduction of metals and particulates will be determined by the concentration of the materials in the oil and/or hydrocarbon feedstock to be treated, along with the concentration of peroxyacid employed.
- the reduction of the metals and particulate content is achieved without any residual peroxyacid in the petroleum oil or feedstock.
- the methods beneficially remove the metals and particulates from the hydrocarbon phase of the emulsion with little or no additional hydrocarbon entrainment into the aqueous phase.
- the methods of using peroxyacids and peroxyacid compositions to remove fine particulates from petroleum oils and refinery feedstocks and/or streams are also useful in various additional applications.
- the methods of mitigation of other metals using the peroxyacids are also useful for minimizing fouling, resolving emulsions and improving waste water quality associated with petroleum oil and refinery feedstocks.
- the peroxyacids can be added to the oil and feedstocks to remove metals and particulates and are effective to improve the waste water from the system due in part to its decomposition into innocuous components (i.e., acetic acid, oxygen, CO 2 and H 2 O).
- the biocidal efficacy of the peroxyacids can also improve the waste water.
- the methods are also useful for enhancing coke quality via contaminate removal.
- Highly crystalline needle coke that can be used for anodes in the aluminum and steel industry is more valuable than fuel grade coke.
- the crystal structure does not form in the presence of metal contaminants. Removing metals with peroxyacids promotes a higher grade of coke.
- the methods are also useful for mitigating fine particulates resulting from use of metal based H 2 S scavengers in aqueous and hydrocarbon streams.
- the methods are also useful for mitigating fine particulates resulting from Aluminum and Zinc based chemical additives.
- the peroxyacids added to the oil and feedstocks to remove metals and particulates beneficially remove various types of particulates from these streams, including solids imparted by the various chemical additives used in the processing of the oil.
- the methods are useful for mitigation of downstream catalyst poisoning and fouling, resulting in elongation of catalyst lifetimes.
- the peroxyacids added to the oil and feedstocks to remove metals and particulates beneficially removes these poisons from the oil and feedstock, taking them out of the downstream product which minimizes downstream catalyst poisoning and fouling.
- various metals and contaminants can poison or deactivate catalysts, it is beneficial to remove the various metals and particulates with the peroxyacids.
- the methods are useful for reducing bacteria in slop oil and crude tanks.
- the combination of removing bacteria, contaminants, and particulates from slop oil and crude tanks is beneficial, as these sources are known to have greater amounts of iron and would therefore benefit from treatment with the peroxyacid.
- EC2472A primary emulsion breaker used to promote oil-water separation
- CORR11540A upstream application sodium gluconate corrosion inhibitor and deoiler
- the portable electric desalter (PED) screening uses an Interav Model EPPT-228 apparatus. The following test method was used:
- Steps 7-10 for each of the remaining samples, placing Sample #2 in the second position, etc. Use a clean blender container for each sample.
- the emulsions are poured into glass tubes (100 ml centrifuge tubes), which are then placed into the heating block of a PED heater unit, the emulsions are resolved with the assistance of constant heating and intermittent application of an electric field.
- the water coalescence was performed as follows:
- Electric field applications are generally ten-minutes in duration and the applied voltage is adjustable between 0-4000 V.
- the first electric field application is normally 3000 V, but the value may vary depending on observations from previous tests.
- the steps permit the resolution of the emulsion to be observed as the volume of free water resolved at fixed intervals during the testing.
- the resulting water phase was collected and submitted for analysis by Inductively Coupled Plasma (ICP).
- ICP Inductively Coupled Plasma
- Bottle testing was performed to identify chemistries most effective at migrating metal content to the water phase following emulsion resolution.
- a known amount of a representative sample of the crude oil and 10-20 mL of distilled water were placed in a series of standard bottles. One of these samples remained untreated and was used as a reference blank while the others were treated with the evaluated chemistries.
- the bottles were agitated simultaneously and replaced in the water bath. At specific times the amount of separated water was observed and recorded. The times of dehydration is according to the retention time in the separations vessels of the plant. Finally, this separated water was removed and submitted for analysis by ICP.
- EC2472A emulsion breaker
- EC6779A peracetic acid
- R-3461 sodium gluconate in water
- the additives were added to either the water or hydrocarbon phase at a concentration of 0, 1000, or 5000 ppm based on the total volume as specified in Table 2.
- the peracetic acid sample used was off-spec and reported at 16% actives.
- the solutions were then heated to 90° C. for 30 minutes and then emulsified using 50% shear power.
- the resulting emulsions were transferred into PED tubes, capped, heated to 120° C. and shocked continuously for 40 minutes with 4000 V.
- the resulting water phase was collected and submitted for ICP analysis.
- the partitioning of metals from the hydrocarbon phase to the water phase was analyzed.
- the concentration of Fe, Ni and Zn found in the water is given in Table 2.
- Percent iron removal to the water phase following addition of 0-1000 ppm of a metals removal agent, is shown in FIG. 2 .
- the brown (hydrocarbon addition) versus blue (water addition) designations are used to define which phase the metal removal agent was charged into prior to emulsification.
- the blank sample which contained no metals removal agent, had considerably less iron in the water at the conclusion of the test than the emulsions treated with EC6779A.
- R-3461 sodium gluconate
- Example #1 A second test was conducted to verify reproducibility of the observed trends in Example #1.
- a sample of light crude oil was used and total metals analysis by ICP is given in Table 3.
- the concentration of iron in the sample was abnormally high. This was likely a result of corrosion of the metal container the sample was stored in.
- Example 1 The only modifications to the Example 1 method were as follows.
- the additives were added to either the water or hydrocarbon phase at a concentration of 500 ppm based on the total volume as specified in Table 4.
- the solutions were then heated to 90 ° C. for 30 minutes and then emulsified using 80% shear power.
- Example 2 Additional testing was completed to compare metal removal achieved by EC6779A, EC6818A, EC2111A and EC2483A.
- Test methodology of Example 1 was followed using 25 ppm of EC2472A and a sample of light crude oil from the United States.
- EC6818A, EC6779A, EC2111A and EC2483A were tested at 1000 ppm each and compared to a blank.
- the emulsions were formed with 10% deionized water at 80% Variac power.
- Total metals analysis by ICP is given in shown in Table 5 and the results shown in Table 6.
- the percent iron removal to the resolved water is shown in FIG. 7 .
- EC6818A demonstrated the strongest performance under these conditions.
- EC2111A and EC2483A did not show competitive performance to the two formulations containing the peroxyacid. The same observation is observed with regards to Zn and Ni removal.
- Example 3 testing was repeated under the same conditions to analyze increased dosages of the chemistries and the effect of R-3461 on EC6818A and EC6779A performance.
- the experimental design and concentration of metals found in the resolved water is shown in Table 7.
- the percent metals removal is substantially higher than expected based on the ICP analysis of the crude oil.
- the blanks show considerably different values for Zn and Ni suggesting the homogeneity of the crude oil sample may be of concern.
- R-3461A did not boost the peroxyacid formulations' performances demonstrating that the use of sodium gluconate is not required in combination with the peroxyacid compositions.
- the two peroxyacid formulations outperformed the carboxylic acids EC2111A (acetic acid) and EC2483A (malic acid) as shown in FIG. 8 .
- Bottle Testing methodology was used to assess efficacy of various metal removal agents. Characterization of the emulsion band formed while processing this slate found 9300 ppm Fe, suggesting the Fe may play a role in emulsion stabilization.
- the crude oil (treated at the refinery with emulsion breaker) was homogenized and then 90 mL aliquots were transferred into five medicine bottles containing 10 mL of distilled water each. Three of the bottles were charged with one of the following metal removal agents at 1000 ppm: EC2111A, EC6779A or CORR11540A. The samples were emulsified using 100% shear and transferred to a heating block set to 120 ° C. The emulsions were then shocked with 4000 V for 20 minutes to facilitate complete emulsion resolution.
- the ability of peroxyacetic acid to remove metals from slop oil was analyzed.
- a sample of slop oil was received in the form of a stable emulsion. The emulsion does not resolve after prolonged periods of quiescent settling in the absence of chemical treatment.
- the sample received was homogenized and sampled into 100 mL aliquots. One aliquot each was treated with 1000 ppm of EC2483A or EC6779A. After 48 hours all the samples contained emulsion except those treated with EC6779A.
- the ability of peroxyacetic acid to remove metals from slop oil was further analyzed.
- the emulsion does not resolve after prolonged periods of quiescent settling in the absence of chemical treatment.
- the sample received was homogenized and sampled into 100 mL aliquots. One aliquot each was treated with 1000 or 5000 ppm of EC2111A (acetic acid) or EC6779A (peracetic acid).
- the treated emulsions were stored for 24 hours.
- the two samples treated with EC6779A contained 1% resolved water.
- the samples were then centrifuged at 140° C. for 30 minutes. Pictures of the resulting resolved emulsion are provided in FIG. 10 .
- the EC6779A samples contained yellow water and significantly more oil free solids were observed at the bottom of the tubes. ICP analysis on the top oil fraction and the resolved water phase are given in Table 10.
- a gallon of a light crude oil from the Gulf Coast was collected for ICP analysis. An aliquot of this crude oil found 25 ppm Fe, 4 ppm Ni, and 1 ppm Zn. The crude oil was homogenized and then 90 mL aliquots were transferred into eight medicine bottles containing 10 mL of distilled water each. The bottles were all charged with 25 ppm EC2472A and the metal removal agents as outlined in Table 11.
- the samples were emulsified using 80% shear and transferred to a heating block set to 120° C. The emulsions were then shocked with 3000 V for 20 minutes to facilitate complete emulsion resolution. The samples were then cooled to ambient temperature. The top oil fraction was sampled for filterable solids (right column of Table 11) and the resolved water phases were collected for analysis by ICP (Table 12).
- R-3461 did not promote metals removal when coupled with the peroxyacids.
- EC6779A and EC6818A outperformed EC2111A and EC2483A. It is unclear which peroxyacid formulation is more effective based on this testing.
Abstract
Description
- This application claims priority under 35 U.S.C. § 119 to Provisional Application U.S. Ser. No. 62/774,625, filed on Dec. 3, 2018, which is herein incorporated by reference in its entirety including without limitation, the specification, claims, and abstract, as well as any figures, tables, or examples thereof.
- The disclosure relates to the use of peroxyacid formulations, including but not limited to peracetic acid and performic acid, for enhancement of downstream processes through removal of soluble and particulate metal complexes from petroleum oils and refinery feedstocks and/or streams. This serves to minimize fouling, decrease the propensity for a solid stabilized emulsion and in turn, improve waste water quality. The methods and compositions are particularly useful for mitigation of heavy metals in petroleum oil and for offsetting potential solid loading resulting from use of a metal based H2S scavenger or other commonly applied metal-based additives. The methods and compositions are also useful for enhancing coke quality via decreased metal concentrations, reducing bacteria in slop oil and crude tanks, as well as reducing downstream catalyst poisoning.
- A survey of a random selection of desalters in the United States found that a significant increase in iron concentration and filterable solids was observed at the desalter interface relative to the raw crude charge. This suggests that solids, sediment or fine particulate, are concentrating at the desalter interface and promoting emulsion stability. If not effectively managed, a decrease in the desalting efficiency of the unit may occur, in addition to other problems such as oil under-carry to the waste water treatment plant and increased slop oil generation. In addition, a number of United States refiners processing light tight oil have reported intermittent “sludges” from iron sulfide contaminated crude oil that have caused negative effects on emulsion stability. At this time there remains a need for an enhanced solids removal agent or demulsifier that can promote partitioning of inorganic particulate, such as iron sulfide, from an emulsion phase to a water phase. This is essential to increase the lifetime of process equipment downstream of the desalter in a refinery, to ensure compliance with environmental regulations in streams processed by refinery waste water treatment plants and to enhance profitability.
- Various methods have been used in an attempt to minimize the negative effect of entrained inorganics in the refining of crude oil. U.S. Pat. Nos. 4,778,589 and 4,789,463 disclose the use of hydroxycarboxylic acids as chemical aids for metals removal in refinery desalting processes. U.S. Pat. No. 4,833,109 to Reynolds discloses the use of dibasic carboxylic acids, particularly oxalic acid, for the removal of divalent metals, including calcium and iron. Wash water addition of hydroxyacids for removing metals during desalting processes is taught in U.S. Pat. Nos. 7,497,943, 4,778,589 and 4,789,463. U.S. Pat. No. 5,271,863 teaches the use of a Mannich reaction product to extract soluble iron and other divalent metal naphthenate complexes from crude oils. U.S. Pat. Nos. 5,114,566 and 4,992,210 teach the removal of corrosive contaminants from crude oil by adding a composition including certain organic amines having a pKb from 2 to 6 and potassium hydroxide to the desalter wash water. The composition is stated to effectively remove chlorides from the crude oil at the desalter. U.S. Pat. No. 5,078,858 suggests the addition of an oxalic or citric acid chelant to the desalter wash water. Likewise, U.S. Pat. No. 4,992,164 also suggests the addition of a chelant, particularly nitrilotriacetic acid, to desalter wash water. U.S. Pat. No. 5,256,304 is directed to the addition of a polymeric tannin material to oily waste water to demulsify oil and flocculate metal ions. U.S. Pat. No. 5,080,779 teaches the use of a chelant in a two stage desalter process for the removal of iron. Other methods involve the use of increased concentrations of emulsion breakers (aka demulsifiers).
- While the methods referenced above have added technical knowledge to the art; in practice they have had limited success. In addition, some methods for removing metals and contaminants result in entrained oil in water that can negatively impact the waste water treatment plant and result in large quantities of slop oil that must be reprocessed. In addition, the various methods are not effective at removing heavy metals such as nickel and vanadium that are organometallically complexed. These inefficiencies indicate that improved methods for the removal of particulates, including metals, from petroleum oil sources are needed.
- Peroxyacids, particularly peracetic acid, have been employed in the oil and gas industry as oilfield antimicrobials in water treatment applications. See for example U.S. Pat. Nos. 2010/0160449 and 7,156,178. In addition, U.S. Pat. No 9,242,879 discloses their use for treatment of drilling fluids, frac fluids, flowback water and disposal water. Application of peroxyacids in the area of commercial well drilling operations have been limited to use as biocides in aqueous systems. Compared to other commercially available biocides, use of peracetic acid has a small environmental footprint, due in part to its decomposition into innocuous components (i.e., acetic acid, oxygen, carbon dioxide and water). There is a lack of teaching to suggest use of the biocidal applications to enhance particulate (including soluble and particulate metal complexes) and/or heavy metal removal from petroleum oil and refinery streams.
- Accordingly, it is an object herein to identify chemical solutions to remove metals from petroleum oil sources. In addition, a further objective of the invention is to develop methods for solids stabilized emulsion control. There have been multiple studies that demonstrate adsorption of surface-modifying components in crude oil to fine particulate, resulting in increased interfacial activity. Increased emulsion stability and viscosity occurs as the concentration of surface-active material at an interface builds. Herein is a disclosure on a mechanism to prevent this phenomenon. Minimizing the concentration of particulate content in crude oil should ultimately facilitate better salt removal and dehydrating efficiency during emulsion resolution processes. Therefore, the peroxyacid formulations can also be considered emulsion breakers in their own right.
- A further objective of the invention is to develop methods for removal of organometallic complexes such as porphyrinic iron, nickel or vanadium or calcium naphthenates. These organometallic compounds are not readily removed by normal desalting practices and can cause coker furnace fouling, finished products outside of specification and deactivation of hydroprocessing catalysts.
- Other objects, advantages and features of the present invention will become apparent from the following description in conjunction with the accompanying Examples.
- The present disclosure is related to the use of peroxyacids compositions and methods of employing peroxyacids for removal of metals and particulate contained in petroleum oil, crude oil, slop oil, and other hydrocarbon streams in various refinery applications. The use of peroxyacid compositions and methods of employing them in various petroleum oil and refinery streams overcomes a significant need in the art for improved methods for removing particulate iron sulfide and zinc sulfide, along with other contaminants. These and other benefits are achieved by the methods disclosed herein.
- In an embodiment, a method for removing particulates in petroleum oil and/or hydrocarbon feedstocks includes the steps of: mixing petroleum oil and/or hydrocarbon feedstock with water to form an emulsion comprising a hydrocarbon phase and a water phase; adding a peroxyacid composition to the emulsion, wherein the peroxyacid causes the particulates to move from the hydrocarbon phase into the water phase; and separating the hydrocarbon phase from the water phase to remove the particulates and the peroxyacid composition from the emulsion. In an embodiment, the peroxyacid oxidizes and chelates the particulates in the emulsion, and wherein the particulates are soluble and particulate metal complexes. In an embodiment, the peroxyacid composition comprises a C1-C22 peroxyacid, a C1-C22 carboxylic acid, and hydrogen peroxide. In embodiments, the peroxyacid is at least one of peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic, peroxyascorbic, peroxyhydroxyacetic, peroxyoxalic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric acid. In embodiments, at least 100 ppm of the peroxyacid is added to the emulsion, or up to about 10,000 ppm of the peroxyacid is added to the emulsion. In embodiments, at least one additional agent that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents is added to the emulsion with the peroxyacid composition. In additional embodiments, the mixture of petroleum oil and/or hydrocarbon feedstock in water is resolved in an electrostatic desalting unit. In additional embodiments, the methods further include adding an effective amount of an emulsion breaker or demulsifier to aid in the separation of the oil from the water phase containing the particulates. In still additional embodiments, the methods further include settling the petroleum oil and/or hydrocarbon feedstock in a tank to enable the water, peroxyacid composition and particulates to settle on the bottom thereof from the petroleum oil and/or hydrocarbon feedstock. In embodiments, the petroleum oil and/or hydrocarbon feedstock is a produced crude oil and is obtained from a pipeline that directs a flow of produced crude oil. In embodiments, the petroleum oil and/or hydrocarbon feedstock once separated from the water phase does not contain any peroxyacid composition. In embodiments, the petroleum oil and/or hydrocarbon feedstock comprise petroleum oil, crude oil, slop oil, and other hydrocarbon streams from a refinery application. In any of the embodiments, the method can exclude the use of phosphoric or phosphorus acids.
- In an embodiment, a crude oil emulsion treatment consists of: crude oil; a peroxyacid composition for transferring metals and particulates from a hydrocarbon phase to a water phase; and a source of water. In embodiments, the treated crude oil emulsion further comprises at least one additional component that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents.
- In an embodiment, an emulsion treatment consists of: petroleum oil, crude oil, slop oil, or another hydrocarbon stream in a refinery application; a peroxyacid composition for transferring metals and particulates from a hydrocarbon phase to a water phase; and a source of water. In embodiments, the treated emulsion further comprises at least one additional component that is a solvent, a corrosion inhibitor, an emulsion breaker or demulsifier, a scale inhibitor, metal chelant, and/or wetting agents.
- While multiple embodiments are disclosed, still other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description, which shows and describes illustrative embodiments of the invention. Accordingly, the detailed description and its Examples are to be regarded as illustrative in nature and not restrictive.
- The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
-
FIG. 1 shows a general diagram of a desalting process. -
FIG. 2 shows a graph of iron removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases. -
FIG. 3 shows a graph of nickel removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases. -
FIG. 4 shows a graph of zinc removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases. -
FIG. 5 shows a graph of iron removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases. -
FIG. 6 shows a graph of zinc removal by peracetic acid, sodium gluconate or combinations thereof in both the hydrocarbon and water phases. -
FIG. 7 is a graph showing iron removal in a resolved water phase by various peroxycarboxylic and carboxylic acids. -
FIG. 8 is a graph showing nickel and zinc removal in a resolved water phase by various chemistries. -
FIG. 9 is a graph showing the amount (ppm) of filterable solids that remained on the top oil fraction after emulsion resolution using various chemistries. -
FIG. 10 is a color photograph of four samples after centrifugation showing the resulting resolved emulsions of EC2111A and EC6779A samples at 1000 ppm and 5000 ppm. - While the above-identified figures set forth several embodiments, other embodiments are also contemplated, as noted in the discussion. In all cases, this disclosure presents the invention by way of representation and not limitation. It should be understood that numerous other modifications and embodiments can be devised by those skilled in the art, which fall within the scope and spirit of the principles of the invention.
- The present invention relates to the methods and application of peroxyacid compositions for particulate and metal removal for improving or enhancing downstream processes for petroleum oil and refinery hydrocarbon feedstocks and streams. The methods of using peroxyacid compositions have many advantages over conventional demetallization technologies. For example, the methods can take place before, after or simultaneous with a desalting step. The effective removal of metals and particulates before a desalting process can significantly minimize the effects of these contaminants on the crude unit and further downstream operations. Having metals and particulates removed before a desalting step then promotes more efficient desalting as well. Benefits can include reduced crude unit corrosion, crude system fouling, energy costs and desalting process demarks, and finished product contamination.
- The embodiments of this invention are not limited to particular methods or peroxyacid compositions, which can vary and are understood by skilled artisans. It is to be further understood that all terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting in any manner or scope. For example, as used in this specification and the appended claims, the singular forms “a,” “an” and “the” can include plural referents unless the content clearly indicates otherwise. Further, all units, prefixes, and symbols may be denoted in its SI accepted form.
- Numeric ranges recited within the specification are inclusive of the numbers defining the range and include each integer within the defined range. Throughout this disclosure, various aspects of this invention are presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges, fractions, and individual numerical values within that range.
- For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6, and decimals and fractions, for example, 1.2, 3.8, 1½, and 4¾. This applies regardless of the breadth of the range.
- So that the present invention may be more readily understood, certain terms are first defined. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which embodiments of the invention pertain. Many methods and materials similar, modified, or equivalent to those described herein can be used in the practice of the embodiments of the present invention without undue experimentation. The preferred materials and methods are described herein. In describing and claiming the embodiments of the present invention, the following terminology will be used in accordance with the definitions set out below.
- The term “about,” as used herein, refers to variation in the numerical quantity that can occur, for example, through typical measuring techniques and equipment, with respect to any quantifiable variable, including, but not limited to, mass, volume, time, distance, wave length, frequency, voltage, current, and electromagnetic field. Further, given solid and liquid handling procedures used in the real world, there is certain inadvertent error and variation that is likely through differences in the manufacture, source, or purity of the ingredients used to make the compositions or carry out the methods and the like. The term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. The term “about” also encompasses these variations. Whether or not modified by the term “about,” the claims include equivalents to the quantities.
- The methods and compositions of the present invention may comprise, consist essentially of, or consist of the components and ingredients of the present invention as well as other ingredients described herein. As used herein, “consisting essentially of” means that the methods, systems, apparatuses and compositions may include additional steps, components or ingredients, but only if the additional steps, components or ingredients do not materially alter the basic and novel characteristics of the claimed methods, systems, apparatuses, and compositions.
- The term “actives” or “percent actives” or “percent by weight actives” or “actives concentration” are used interchangeably herein and refers to the concentration of those ingredients involved expressed as a percentage minus inert ingredients such as water or salts.
- As used herein, the terms “preferred” and “preferably” refer to embodiments that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.
- As used herein, the term “waters” includes water in industrial and/or energy service applications. Waters in industrial and/or energy service applications include for example: aquifer water, river water, sea water, produced water, fresh water, water for injection, secondary flooding water, hot water or feedwater, ethanol/bio-fuels process waters, pretreatment and utility waters, membrane system liquids, ion-exchange bed liquids, water used in the process/manufacture of paper, ceiling tiles, fiber board, microelectronics, E-coat liquids, electrodeposition liquids, process cleaning liquids, oil exploration services liquids, oil well completion fluids, oil well workover fluids, drilling additive fluids, oil fracturing fluids, oil and gas wells, flowline water systems, natural gas water systems, or the like. The term “weight percent,” “wt. %,” “wt-%,” “percent by weight,” “% by weight,” and variations thereof, as used herein, refer to the concentration of a substance as the weight of that substance divided by the total weight of the composition and multiplied by 100.
- Peroxyacid Compositions
- The methods employ at least one peroxyacid or a peroxyacid composition. Without being limited to a particular mechanism, peroxyacids and peroxyacid compositions are able to increase the hydrophilicity of particulate materials (including soluble and particulate metal complexes) in petroleum oil and refinery streams to enhance their removal from the oil/water emulsions. This beneficially allows the acid to oxidize and chelate organometallic complexes and metal-based particulates, which is distinct from use of other acids (i.e. acetic, phosphoric, or phosphorus acids which are excluded from the peroxyacids and peroxyacid compositions disclosed herein) which are only able to chelate reactive metal complexes. The approximate amount of peroxyacid required to achieve the desired amount of metal or particulate removal from an oil stream can be determined by one skilled in the art by taking into account characteristics of the stream being treated. In an aspect, the concentration of peroxyacid sufficient to demetallize a petroleum oil or refinery stream can range from 1 ppm to 10,000 ppm, between about 1,000 ppm and about 5,000 ppm, or ranges there between. In an aspect, the concentration of peroxyacid sufficient to demetallize a petroleum oil or refinery stream can be at least about 100 ppm, at least about 1,000 ppm, at least about 2,000 ppm, at least about 3,000 ppm, at least about 4,000 ppm, at least about 5,000 ppm, at least about 6,000 ppm, at least about 7,000 ppm, at least about 8,000 ppm, at least about 9,000 ppm, at least about 10,000 ppm, or ranges there between.
- Suitable peroxyacids include both organic and inorganic peroxyacids as set forth herein. Organic peroxyacids, include for example peroxycarboxylic acids that generally have the formula RCO3H, where, for example, R is defined as an alkyl, alkenyl, alkyne, acyclic, alicyclic group, aryl, arylalkyl, cycloalkyl, aromatic, heteroaryl, heterocyclic group, or hydrogen. The R-group can be saturated or unsaturated as well as substituted or unsubstituted. Peroxyacids can be made, for example, by the direct action of an oxidizing agent on a carboxylic acid, by auto-oxidation of aldehydes, or from acid chlorides, and hydrides, or carboxylic anhydrides with hydrogen or sodium peroxide. Any suitable C1-C26 peroxyacid, such as a peroxycarboxylic acid can be used. In some embodiments, the C1-C26 percarboxylic acid is a C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, and/or C26 percarboxylic acid. In some embodiments, a C1-C22 peroxyacid is preferred, or combinations thereof.
- Peroxyacids may include short chain and/or medium chain peroxyacids. As used herein, a “short chain peracid” refers to a peroxyacid having a carbon chain between 1 and 4 carbons. Short chain peracids have the benefit of often being highly miscible in water at 25° C. Examples of short chain carboxylic acids include formic acid, acetic acid, propionic acid, and butyric acid. Peroxyacetic (or peracetic) acid is a peroxyacid having the formula: CH3COOOH. Generally, peroxyacetic acid is a liquid having an acrid odor at higher concentrations and is freely soluble in water, alcohol, ether, and sulfuric acid. Peroxyacetic acid can be prepared through any number of methods known to those of skill in the art including preparation from acetaldehyde and oxygen in the presence of cobalt acetate. A solution of peroxyacetic acid can be obtained by combining acetic acid with hydrogen peroxide. In a preferred embodiment, the compositions of the invention employ a C1 to C4 peroxyacid.
- As used herein, the phrase “medium chain peracid” refers to a peroxyacid having a carbon chain between 5 and 22 carbons in length. Further as used herein, the phrase “medium chain carboxylic acid” can refer to a carboxylic acid that has a critical micellization concentration greater than 1 mM in aqueous buffers at neutral pH. It is also common for medium chain carboxylic acids to have an unpleasant odor. Medium chain carboxylic acids exclude carboxylic acids that are infinitely soluble or miscible with water at 20° C. Medium chain carboxylic acids include carboxylic acids with boiling points (at 760 mm Hg pressure) of 180 to 300° C. In an embodiment, medium chain carboxylic acids include carboxylic acids with boiling points (at 760 mm Hg pressure) of 200 to 300° C. In an embodiment, 20 medium chain carboxylic acids include those with solubility in water of less than 1 g/L at 25° C. Examples of medium chain carboxylic acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, and dodecanoic acid.
- Peroxyacids useful in the methods described herein include meta-chloroperoxybenzoic, peroxyformic, peroxyacetic, peroxypropionic, peroxybutanoic, peroxypentanoic, peroxyhexanoic, peroxyheptanoic, peroxyoctanoic, peroxynonanoic, peroxydecanoic, peroxyundecanoic, peroxydodecanoic, or the peroxyacids of their branched chain isomers, peroxylactic, peroxymaleic, peroxyascorbic, peroxyhydroxyacetic, peroxyoxalic, meta-chloroperoxybenzoic, peroxymalonic, peroxysuccinic, peroxyglutaric, peroxyadipic, peroxypimelic and peroxysubric acid and mixtures thereof. Inorganic peroxyacids such as peroxymonosulfuric acid (Caro's acid) are not excluded from the peroxyacid and/or peroxyacid compositions.
- In some embodiments more than one peroxyacid can be employed. For example, in some embodiments, the composition includes one or more C1 to C4 peroxyacids and one or more C5 to C22 peroxyacids. In one aspect of the invention the ratio of short chain peroxyacid to medium chain peroxyacid can be about 1:1 to about 10:1.
- As referred to herein, a peroxyacid composition also includes an organic acid (i.e. corresponding carboxylic acid) and an oxidizing agent. In various aspects, the peroxyacid composition can be formed by an organic acid and an oxidizing agent. The compositions can be pre-formed. In other aspects, peroxyacid compositions may be generated in situ. Additional description of exemplary in situ methods for peroxyacids is provided for example in U.S. Pat. Nos. 9,845,290, 9,518,013, 8,846,107 and 8,877,254, which are herein incorporated by reference in its entirety.
- Oxidizing Agent
- The peroxyacid compositions may also include an oxidizing agent. Most often the oxidizing agent is hydrogen peroxide. Hydrogen peroxide, H2O2, provides the advantages of having a high ratio of active oxygen because of its low molecular weight (34.014 g/mole) and by being compatible with numerous substances that can be treated by methods of the invention because it is a weakly acidic, clear, and colorless liquid. Another advantage of hydrogen peroxide is that it decomposes into innocuous water and oxygen.
- The peroxyacid compositions can include any desired ratio of hydrogen peroxide. In some embodiments, the hydrogen peroxide in the percarboxylic acid composition has a concentration from about 0.5 wt-% to about 25 wt-%, preferably from about 0.5 wt-% to about 10 wt-%. In other embodiments, the hydrogen peroxide has a concentration from about 1 wt-% to about 2 wt-%. In still other embodiments, the hydrogen peroxide has a concentration at about 0.5 wt-%, 1 wt-%, 2 wt-%, 3 wt-%, 4 wt-%, 5 wt-%, 6 wt-%, 7 wt-%, 8 wt-%, 9 wt-%, or 10 wt-%. In yet other embodiments, the hydrogen peroxide has a concentration at about 1 wt-%, 1.1 wt-%, 1.2 wt-%, 1.3 wt-%, 1.4 wt-%, 1.5 wt-%, 1.6 wt-%, 1.7 wt-%, 1.8 wt-%, 1.9 wt-%, 2 wt-%, 2.1 wt-%, 2.2 wt-%, 2.3 wt-%, 2.4 wt-%, 2.5 wt-%, 2.6 wt-%, 2.7 wt-%, 2.8 wt-%, 2.9 wt-%, 3 wt-%, 3.1 wt-%, 3.2 wt-%, 3.3 wt-%, 3.4 wt-%, 3.5 wt-%, 3.6 wt-%, 3.7 wt-%, 3.8 wt-%, 3.9 wt-%, or 4 wt-%.
- Additional oxidizing agents include for example, the following types of compounds or sources of these compounds, or alkali metal salts including these types of compounds, or forming an adduct therewith: hydrogen peroxide, urea-hydrogen peroxide complexes or hydrogen peroxide donors of: group 1 (IA) oxidizing agents, for example lithium peroxide, sodium peroxide; group 2 (IIA) oxidizing agents, for example magnesium peroxide, calcium peroxide, strontium peroxide, barium peroxide; group 12 (IIB) oxidizing agents, for example zinc peroxide; group 13 (IIIA) oxidizing agents, for example boron compounds, such as perborates, for example sodium perborate hexahydrate of the formula Na2[B2(O2)2(OH)4]·6H2O (also called sodium perborate tetrahydrate); sodium peroxyborate tetrahydrate of the formula Na2B2(O2)2[(OH)4]·4H2O (also called sodium perborate trihydrate); sodium peroxyborate of the formula Na2[B2(O2)2(OH)4] (also called sodium perborate monohydrate); group 14 (IVA) oxidizing agents, for example persilicates and peroxycarbonates, which are also called percarbonates, such as persilicates or peroxycarbonates of alkali metals; group 15 (VA) oxidizing agents, for example peroxynitrous acid and its salts; peroxyphosphoric acids and their salts, for example, perphosphates; group 16 (VIA) oxidizing agents, for example peroxysulfuric acids and their salts, such as peroxymonosulfuric and peroxydisulfuric acids, and their salts, such as persulfates, for example, sodium persulfate; and group VIIa oxidizing agents such as sodium periodate, potassium perchlorate. Other active inorganic oxygen compounds can include transition metal peroxides; and other such peroxygen compounds, and mixtures thereof.
- Methods of Use
- Methods of using peroxyacids (or peroxyacid compositions) to treat petroleum oils and hydrocarbon feedstocks and/or streams are particularly useful for mitigating deleterious effects caused by heavy metal concentrations, emulsion stability or high particulate content. As referred to herein, the feedstocks include any hydrocarbon feedstock including for example crude oil, slop oil, heavy residua, atmospheric or vacuum residua, deasphalted oils derived from the crude oil or residua, shale oil, liquified coal and tar sand effluent, and the like and blends thereof. As used herein, “removing” the metals and/or particulates from the petroleum oil and feedstocks (namely the hydrocarbon phase) is meant to include any and all partitioning, sequestering, separating, transferring, eliminating, dividing, removing, of one or more metal and/or particulate from the hydrocarbon phase to any extent.
- In a particular embodiment particulates can include inorganic fines that are naturally occurring in crude oil such as silt, clays, silicates and metal oxides. These inorganic materials may not reactive with the peroxyacids but can be removed indirectly during an emulsion resolution process treated with the additive (vide infra). Particulates can also include alkali metal salts, including but not limited to, calcium carbonate (CaCO3), calcium sulfate (CaSO4), iron oxides (Fe2O3 and Fe3O4), and barium sulfate (BaSO4).
- In a particular embodiment, other heavy metals can include, but are not limited to, metal sulfides, metal chlorides, organo-porphyrins or other organometallic complexes that may react with the peroxyacid. Metals suitable for removal using the process of this invention (soluble or water insoluble) include, but are not limited to those of
Groups - In a particular embodiment, refinery applications include, but are not limited to raw crude processing, desalting, tankage treatment and dehydration, slop oil resolution and mitigation, FCC desalter performance enhancement, and waste water contaminate removal and processing.
- The methods of employing peroxyacids to remove fine particulates and metals from petroleum oils and refinery feedstocks includes applying or adding a peroxyacid to a wash water source, a petroleum oil and/or hydrocarbon feedstock. As referred to herein, this includes, but is not limited to, crude oil, slop oil, and water in oil or oil in water emulsions. The oil or feedstock to be treated should preferably be in a liquid state at the selected process conditions in order to facilitate contact between the oil and the aqueous extractant (i.e. the peroxyacid and/or water). As one skilled in the art appreciates this may be accomplished by heating the oil or by the addition of a suitable solvent, e.g. a lower boiling hydrocarbon oil, as needed. The petroleum oil or feedstock to be treated is delivered to a pipeline with a heat exchanger. In such embodiments, a water supply line connects to the flow of heated oil and is delivered with the oil.
- The methods may comprise, consist of and/or consist essentially of one or more of the following steps: add water and peroxyacid to a petroleum oil or hydrocarbon feedstock; add a peroxyacid to an emulsion of oil (hydrocarbon phase) and water (aqueous/water phase); water-wet particulates; oxidize metals; chelate a metal; separate the water phase containing residual peroxyacid, water soluble metal complexes, and particulates from the hydrocarbon phase. In an embodiment, the peroxyacid can be added to an emulsion formed of a hydrocarbon phase and a water phase without further addition of water.
- In another embodiment, the methods of adding a peroxyacid to the petroleum oil or feedstock may precede a desalting step. A refinery's desalting unit is designed to remove entrained water, water-soluble contaminants and oil-insoluble particulates from crude oil. Crude oil is defined here as any hydrocarbon stream entering a refinery that will be processed through the desalter. This crucial step of the refining process is necessary to extend the lifetime of process equipment downstream of the unit, render the crude oil less corrosive, protect downstream refinery equipment from fouling, and to maximize throughput. The desalter achieves this by (I) providing crude oil; (II) adding wash water to the crude oil and mixing the two phases together to form an emulsion; (III) subsequently breaking the emulsion that is formed to provide an aqueous phase and a hydrocarbon phase containing a lower concentration of salt, particulate and metals. The resolved hydrocarbon phase is commonly drawn off the top of the unit and sent to a fractionator tower. The water phase containing water-soluble metal salt compounds and sediment is discharged out the bottom of the unit and sent to a waste water treatment plant for processing. A general schematic of this process is given in
FIG. 1 . Desalting is traditionally enhanced by application of a high voltage electric field, heat, and by the addition of chemical additives such as emulsion breakers, solids-removal agents, and coagulants. - When effective desalting is achieved, entrained water in the crude oil will coalesce with the wash water and gravity settle to the bottom of the unit. This process is used to remove water-soluble salts such as sodium chloride, allow sediment to gravity settle, and to “water-wet” particulate. These three benefits are further elaborated on in the following discussion:
- Benefit of Removal of Residual Salts. Water soluble salts in crude oil are typically chloride, sulfate or carbonate salts of sodium, magnesium, or calcium. If the salts are not effectively removed to the water phase, scale may result. This will reduce throughput and potentially increase operating costs. In addition, under the process conditions downstream of the desalter the salts will hydrolyze to form their acid analog, which will accelerate corrosion rates in the process vessels downstream of the unit and compromise their structural integrity.
- Benefits of Removal of Sediment. Sediment is largely composed of naturally occurring materials, such as silicas, clays, asphaltenes, and metal oxides, resulting from the geologic formation from which the crude oil was extracted or from corrosion. This material may gravity settle in the desalter if the particle size of the sediment and conditions within the unit (emulsion viscosity, crude oil retention times etc.) are favorable. Effective removal of this water-insoluble material will increase throughput by diminishing fouling rates and will increase profitability for the refiner by decreasing the frequency at which heat exchangers must be cleaned.
- Benefits of Removal of Fine Particulate. Fine particulate, also known as suspended solids, are hydrocarbon and water insoluble inorganics that are too small to gravity settle in the desalter. These inorganics are largely introduced into crude oil from the geological formation (sand, silt, alkali metal salts, etc.), from corrosion processes (FeS) or from upstream additives (metal based H2S scavengers, aluminum-based coagulants, etc.). When suspended in a hydrocarbon phase, particulate can lead to operational challenges. These challenges include plugged filters, low grade coke quality, increased fouling in process equipment, and shortened lifetime of fluid catalytic cracking (FCC) catalysts. In addition, fine particulate can act as an emulsifier and exacerbate emulsion stability at the desalter, which may lead to a decrease in desalting efficiency and/or an increase in the volume of slop oil generated.
- The crude oil aforementioned and desalter emulsions may have high concentrations of metals, including iron sulfide, and the methods disclosed herein beneficially removes those metals and particulates more efficiently than in a typical desalting operation. In addition, the peroxyacid formulation may enhance overall desalter performance by promoting increased removal of salt, sediment and fine particulate from the hydrocarbon phase.
- In an embodiment, the peroxyacid is provided or introduced (e.g. injected) into a pipe and/or tank upstream of the desalter to contact the hydrocarbon. In a further aspect, the peroxyacid is preferably injected upstream of a location where the treated feed will have adequate settling time to allow the water and hydrocarbon phases to resolve and the particulates to migrate to the water phase.
- In another embodiment, the methods of adding a peroxyacid to the petroleum oil or feedback may be before, simultaneous, or after the addition of wash water to the crude oil. The method of adding a peroxyacid may also be directly into a water phase.
- In another embodiment, the methods may also include the step of adding an effective amount of at least one additional agent or component that is water or a solvent, a corrosion inhibitor, a demulsifier (such as an oxyalkylate), a scale inhibitor, metal chelants, wetting agents and mixtures thereof. In a preferred embodiment, the methods may also include the step of adding an effective amount of an emulsion breaker (i.e. demulsifier) to aid in the separation of the oil from the water phase containing the particulates.
- In another embodiment, the methods of adding a peroxyacid to the petroleum oil or feedstock may precede a tankage dehydration step. This may relate to dehydration of a hydrocarbon or petroleum oil stream entering a refinery tank farm or static settling of an emulsion downstream of the desalter.
- The contact time for the peroxyacid will vary depending upon the process and wash water, petroleum oil and/or hydrocarbon feedstock to be treated. Here, the peroxyacid is simply added and mixed with the oil, and then is removed along with the water phase and particulates. In an embodiment, the amount of peroxyacid added to the petroleum oil or feedstock will depend upon the oil or feedstock to be treated. As one skilled in the art appreciates, the amount of metals (e.g. iron) or particulates in the oil or feedstock can vary significantly. For example, slop oil may have a higher concentration of metals and particulates than crude oil. In an aspect, the concentration of peroxyacid provided is between about 1 ppm and about 50,000 ppm, between about 1,000 ppm and about 30,000 ppm, between about 1,000 ppm and about 20,000 ppm, or ranges there between. In an aspect, the concentration of peroxyacid is at least about 1 ppm, at least about 1,000 ppm, at least about 2,000 ppm, at least about 3,000 ppm, at least about 4,000 ppm, at least about 5,000 ppm, at least about 6,000 ppm, at least about 7,000 ppm, at least about 8,000 ppm, at least about 9,000 ppm, at least about 10,000 ppm, or ranges there between.
- In an embodiment, one or more demulsifiers are added to the crude oil or wash water. The peroxyacid may also act as a demulsifier.
- In an aspect, the methods beneficially reduce the metals and particulate content in the petroleum oil or refinery stream by at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 99%, or complete removal. As one skilled in the art will ascertain the percentage of reduction of metals and particulates will be determined by the concentration of the materials in the oil and/or hydrocarbon feedstock to be treated, along with the concentration of peroxyacid employed. In a further aspect, the reduction of the metals and particulate content is achieved without any residual peroxyacid in the petroleum oil or feedstock. In a further aspect, the methods beneficially remove the metals and particulates from the hydrocarbon phase of the emulsion with little or no additional hydrocarbon entrainment into the aqueous phase.
- Additional Methods of Use
- The methods of using peroxyacids and peroxyacid compositions to remove fine particulates from petroleum oils and refinery feedstocks and/or streams are also useful in various additional applications. The methods of mitigation of other metals using the peroxyacids are also useful for minimizing fouling, resolving emulsions and improving waste water quality associated with petroleum oil and refinery feedstocks. The peroxyacids can be added to the oil and feedstocks to remove metals and particulates and are effective to improve the waste water from the system due in part to its decomposition into innocuous components (i.e., acetic acid, oxygen, CO2 and H2O). Moreover, the biocidal efficacy of the peroxyacids can also improve the waste water.
- The methods are also useful for enhancing coke quality via contaminate removal. Highly crystalline needle coke that can be used for anodes in the aluminum and steel industry is more valuable than fuel grade coke. The crystal structure does not form in the presence of metal contaminants. Removing metals with peroxyacids promotes a higher grade of coke.
- The methods are also useful for mitigating fine particulates resulting from use of metal based H2S scavengers in aqueous and hydrocarbon streams. The methods are also useful for mitigating fine particulates resulting from Aluminum and Zinc based chemical additives. The peroxyacids added to the oil and feedstocks to remove metals and particulates beneficially remove various types of particulates from these streams, including solids imparted by the various chemical additives used in the processing of the oil.
- In addition, the methods are useful for mitigation of downstream catalyst poisoning and fouling, resulting in elongation of catalyst lifetimes. The peroxyacids added to the oil and feedstocks to remove metals and particulates beneficially removes these poisons from the oil and feedstock, taking them out of the downstream product which minimizes downstream catalyst poisoning and fouling. As various metals and contaminants can poison or deactivate catalysts, it is beneficial to remove the various metals and particulates with the peroxyacids.
- Still further the methods are useful for reducing bacteria in slop oil and crude tanks. In an aspect, the combination of removing bacteria, contaminants, and particulates from slop oil and crude tanks is beneficial, as these sources are known to have greater amounts of iron and would therefore benefit from treatment with the peroxyacid.
- All publications and patent applications in this specification are indicative of the level of ordinary skill in the art to which this invention pertains. All publications and patent applications are herein incorporated by reference to the same extent as if each individual publication or patent application was specifically and individually indicated as incorporated by reference.
- The foregoing may be better understood by reference to the following examples, which are presented for purposes of illustration and are not intended to limit the scope of this invention. It should be understood that these Examples, while indicating certain embodiments of the invention, are given by way of illustration only. From the above discussion and these Examples, one skilled in the art can ascertain the essential characteristics of this invention, and without departing from the spirit and scope thereof, can make various changes and modifications of the embodiments of the invention to adapt it to various uses and conditions. Thus, various modifications of the embodiments of the invention, in addition to those shown and described herein, will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims. The following materials were used in the experiments set forth in the Examples:
- EC6818A—15% peracetic acid with 10% hydrogen peroxide in water
- EC6779A—21% peracetic acid with 3% hydrogen peroxide in water
- EC2472A—primary emulsion breaker used to promote oil-water separation
- R-3461—30% sodium gluconate in water
- EC2111A—glacial acetic acid
- EC2483A—malic acid
- EC2580A—heavy metal removal agent (polymeric material)
- EC2345A—reverse emulsion breaker/flocculent
- CORR11540A—upstream application sodium gluconate corrosion inhibitor and deoiler
- EC9008B—anionic and non-anionic surfactant blend.
- The portable electric desalter (PED) screening uses an Interav Model EPPT-228 apparatus. The following test method was used:
- Method for replicating refinery desalting applications were employed by preparing water-in-oil emulsions by blending a fixed volume of water and crude oil under controlled conditions. The emulsion was prepared as follows:
- 1. Charge 8 prescription bottles (6 oz.) with 10 mL of deionized water. Add the metals removal agent directly to the water phase (dosage to be based on total volume of water+crude oil).
- 2. Gently layer raw crude oil into each prescription bottle so that the total volume of liquid is equivalent to 100 mL. Add the appropriate metals removal agent directly to the hydrocarbon phase (dosage to be based on total volume of water+crude oil).
- 3. Use a microliter syringe to add the appropriate amount of emulsion breaker formulation to the hydrocarbon.
- 4. Cap the bottles loosely to prevent over-pressurization in the heated water bath. Place the containers into a water bath and equilibrate to 90° C. for at least 20 minutes. Confirm the PED heater block is set to 90° C. and place the PED tubes inside.
- 5. After 20 minutes of heating, pour the contents of
Sample # 1 into the first blender jar. Attach a blender cap to prevent overflow during mixing. - 6. Adjust the output voltage of the rheostat to an appropriate setting (e.g., 50%-100% of full power).
- 7. De-gas the emulsion sample by turning the blended ON and OFF as quickly as possible. Immediately after degassing, turn ON the blender and emulsify the sample for exactly 10 seconds. Warning: Adequate de-gassing and use of the blender cap should prevent blender contents from foaming over the rim of the container.
- 8. Pour the contents of the blender into the first PED tube. Attach the electrode cap and tighten firmly by hand. Place the sample tube in the rack in the
Sample # 1 position. - 9. Repeat Steps 7-10 for each of the remaining samples, placing Sample #2 in the second position, etc. Use a clean blender container for each sample.
- Once the emulsions are poured into glass tubes (100 ml centrifuge tubes), which are then placed into the heating block of a PED heater unit, the emulsions are resolved with the assistance of constant heating and intermittent application of an electric field. The water coalescence was performed as follows:
- 1. When all tubes have been blended, place them inside the heating block in the appropriate positions. Increase the set temperature of the heating block from 90° C. to 120° C.
- 2. Place the electrode assembly cover plate over the heater block to complete the electrical connection.
- 3. Adjust the voltage control dial to the appropriate output voltage to apply electric fields. Electric field applications are generally ten-minutes in duration and the applied voltage is adjustable between 0-4000 V. The first electric field application is normally 3000 V, but the value may vary depending on observations from previous tests.
- 4. Current flow to the PED tubes is detected during the electric field applications by toggling the eight individual switches located directly below the ammeter. Upon toggling each switch the needle should briefly deflect on the ammeter and return to the rest value.
- 5. After the first electric field application, confirm that voltage is no longer being applied by visual inspection of the warning light. Adjust the voltage control to the zero setting and remove the electrode assembly cover plate.
- 6. The volume of free water (in milliliters) that has separated in each PED tube after 10 minutes have elapsed is recorded. Free water is recorded as the highest volume increment where a flashlight beam is transmitted through the PED tube. If most of the water has resolved remove the tubes from the heater block. If less than 10 mL of water is observed repeat the voltage application until all the tubes have resolved most of the added water.
- 7. Transfer the PED tubes to a cooling rack.
- 8. Once the temperature is below 90° C. the tubes can be opened. Sample the water phase with glass pipettes taking care to leave behind as much oil as possible. It may be necessary to repeat the extraction.
- 9. Submit the water samples for analysis via ICP.
- The steps permit the resolution of the emulsion to be observed as the volume of free water resolved at fixed intervals during the testing. At the end of each test the resulting water phase was collected and submitted for analysis by Inductively Coupled Plasma (ICP).
- The following test method was used in the Examples for a Bottle Testing:
- Bottle testing was performed to identify chemistries most effective at migrating metal content to the water phase following emulsion resolution. A known amount of a representative sample of the crude oil and 10-20 mL of distilled water were placed in a series of standard bottles. One of these samples remained untreated and was used as a reference blank while the others were treated with the evaluated chemistries. The bottles were agitated simultaneously and replaced in the water bath. At specific times the amount of separated water was observed and recorded. The times of dehydration is according to the retention time in the separations vessels of the plant. Finally, this separated water was removed and submitted for analysis by ICP.
- The methods for emulsion preparation were as follows:
- 1. Charge medicine bottles with 100 mL the emulsion of interest.
- 2. Determine the relative amount of water in each emulsion by conducting a BS&W test per ASTM D-4007.
- 3. Use a microliter syringe to add the appropriate amount of emulsion breaker formulation to the emulsion.
- 4. Use a microliter syringe to add the appropriate amount of metals removal agent to the emulsion
- 5. Cap the bottles and shake all the samples simultaneously on a mechanical shaker.
- 6. If the emulsion requires heat for treatment, place the bottles in a water bath at the system temperature. Carefully loosen the caps on the bottles before placing in the water bath.
- 7. Observe and record the water drop, interface and water quality observed in each bottle. When most of the water has resolved sample it with a glass pipette, taking care to leave as much oil behind as possible.
- 8. Sample the water again if necessary, to remove as much oil as possible.
- 9. Submit the water samples for analysis by ICP.
- Testing was conducted using the Portable Electric Desalter Screening methods to assess whether peracetic acid, sodium gluconate or combinations of the two additives could effectively migrate iron containing material from a crude oil fraction into a water phase. Metal content of a heavy crude oil sample, as reported by ICP, is shown in Table 1.
-
TABLE 1 Total Metal (ppm) Soluble Aluminum (Al) 4.0 0.3 Barium (Ba) 2.0 0.1 Calcium (Ca) 14.5 2.9 Chromium (Cr) 0.2 0.1 Cobalt (Co) 0.4 0.4 Copper (Cu) 1.2 0.2 Iron (Fe) 40.3 4.5 Magnesium (Mg) 3.1 0.8 Manganese (Mn) 0.7 0.2 Molybdenum (Mo) 0.6 0.4 Nickel (Ni) 37.3 37.3 Potassium (K) 14.1 2.3 Sodium (Na) 64.2 8.7 Strontium (Sr) 0.9 0.1 Titanium (Ti) 0.8 0.3 Vanadium (V) 165.0 165.0 Zinc (Zn) 1.9 0.7 - 90 mL of the crude oil, 10 mL of deionized water and 50 ppm of EC2472A (emulsion breaker) were added to 160 mL medicine bottles. EC6779A (peracetic acid) or R-3461 (sodium gluconate in water) were screened. The additives were added to either the water or hydrocarbon phase at a concentration of 0, 1000, or 5000 ppm based on the total volume as specified in Table 2. The peracetic acid sample used was off-spec and reported at 16% actives. The solutions were then heated to 90° C. for 30 minutes and then emulsified using 50% shear power. The resulting emulsions were transferred into PED tubes, capped, heated to 120° C. and shocked continuously for 40 minutes with 4000 V. The resulting water phase was collected and submitted for ICP analysis. The partitioning of metals from the hydrocarbon phase to the water phase was analyzed. The concentration of Fe, Ni and Zn found in the water is given in Table 2.
-
TABLE 2 Ratio of FeS Concentration EC6779A to Dissolver and phase the Medicine R-3461 Total Dosage Fe dissolver Iron (Fe, Nickel (Ni, Zinc (Zn, Bottle Solution (ppm) was added to: ppm) ppm) ppm) 3 1:1 5000 hydrocarbon 141 309 12.9 4 1:3 5000 hydrocarbon 105 71.2 6.98 5 0:1 5000 hydrocarbon 51.8 6.03 0.26 7 3:1 5000 water 109 279 14.9 8 NA 0 50.5 34.4 1.16 9 1:1 5000 water 129 624 6.01 10 1:3 5000 water 106 220 5.23 11 0:1 5000 water 57.3 140 0.63 12 1:0 1000 hydrocarbon 88.4 152 3.32 13 3:1 1000 hydrocarbon 79.1 45.5 2.27 14 1:1 1000 hydrocarbon 77.3 178 3.01 15 1:3 1000 hydrocarbon 64 130 1.12 16 NA 0 11.6 0.69 <0.25 17 0:1 1000 hydrocarbon 8.05 56.3 <0.25 18 1:0 1000 water 85.1 139 4.69 19 3:1 1000 water 80.4 92.6 3.4 20 1:1 1000 water 68.4 34 0.98 21 1:3 1000 water 59.8 27 0.93 22 0:1 1000 water 18.8 25.7 <0.25 - Percent iron removal to the water phase, following addition of 0-1000 ppm of a metals removal agent, is shown in
FIG. 2 . The brown (hydrocarbon addition) versus blue (water addition) designations are used to define which phase the metal removal agent was charged into prior to emulsification. The blank sample, which contained no metals removal agent, had considerably less iron in the water at the conclusion of the test than the emulsions treated with EC6779A. By itself, R-3461 (sodium gluconate) was not effective at facilitating migration of iron to the hydrocarbon phase. - Migration of Fe to the water phase is shown as proportional to the overall dosage of EC6779A. 5000 ppm treats with EC6779A and 33% R-3461 solution gave upwards of 30% iron removal. Similar observations were observed with regards to Ni and Zn removal as shown in
FIG. 3 andFIG. 4 , respectively. - A second test was conducted to verify reproducibility of the observed trends in
Example # 1. A sample of light crude oil was used and total metals analysis by ICP is given in Table 3. The concentration of iron in the sample was abnormally high. This was likely a result of corrosion of the metal container the sample was stored in. -
TABLE 3 Total Metal ppm Aluminum (Al) 5.79 Barium (Ba) 12.3 Calcium (Ca) 53.6 Chromium (Cr) 0.131 Cobalt (Co) <0.012 Copper (Cu) 6.73 Iron (Fe) 170 Magnesium (Mg) 13.2 Manganese (Mn) 2.14 Molybdenum (Mo) 0.06 Nickel (Ni) 1.76 Potassium (K) 7.36 Sodium (Na) 199 Strontium (Sr) 1.92 Titanium (Ti) 0.159 Vanadium (V) 2.99 Zinc (Zn) 10.7 - The only modifications to the Example 1 method were as follows. The additives were added to either the water or hydrocarbon phase at a concentration of 500 ppm based on the total volume as specified in Table 4. The solutions were then heated to 90 ° C. for 30 minutes and then emulsified using 80% shear power. The concentration of Fe, Al, Ni, and
- Zn found in the water is tabulated in Table 4.
-
TABLE 4 Al Fe Ni Zn Bottle Added to Ratio of EC6779A to R-3461 (ppm) (ppm) (ppm) (ppm) 1 hydrocarbon EC6779A 97.8 93.4 198 44.3 2 hydrocarbon 3 part EC6779A to 1 part R-3461 33.5 138 210 47.5 3 hydrocarbon 1 part EC6779A to 1 part R-3461 3.76 118 168 18.7 4 hydrocarbon 1 part EC6779A to 3 part R-3461 8.97 102 82 13.1 5 hydrocarbon R-3461 9.36 7.94 2.71 0.46 6 water EC6779A 18.9 114 128 49.2 7 water 3 part EC6779A to 1 part R-3461 21.5 108 155 40.3 8 blank not detected 2.28 4.42 not detected 9 water 1 part EC6779A to 1 part R-3461 11.4 125 88.4 40 10 water 1 part EC6779A to 3 part R-3461 5.69 137 5.62 11.7 11 water R-3461 3.56 10.2 1.15 0.45 12 blank not detected 1.9 1.01 not detected - The percent iron and zinc removal results, based on the total concentration in the light crude, are broken out in
FIG. 5 andFIG. 6 , respectively. EC6779A was again observed to help facilitate Zn, Fe, and Al removal. Overall, there was a significant increase in the concentration of the metals in the water phase relative to the blank or R-3461 treated emulsions. - Additional testing was completed to compare metal removal achieved by EC6779A, EC6818A, EC2111A and EC2483A. Test methodology of Example 1 was followed using 25 ppm of EC2472A and a sample of light crude oil from the United States. EC6818A, EC6779A, EC2111A and EC2483A were tested at 1000 ppm each and compared to a blank. The emulsions were formed with 10% deionized water at 80% Variac power. Total metals analysis by ICP is given in shown in Table 5 and the results shown in Table 6.
-
TABLE 5 WTS metal ppm Aluminum (Al) 0.515 Barium (Ba) 0.073 Calcium (Ca) 4.43 Chromium (Cr) 0.046 Cobalt (Co) <0.012 Copper (Cu) 0.139 Iron (Fe) 24.5 Magnesium (Mg) 1.18 Manganese (Mn) 0.117 Molybednum (Mo) <0.025 Nickel (Ni) 3.7 Potassium (K) 0.733 Sodium (Na) 13.7 Strontium (Sr) 0.084 Titanium (Ti) 0.055 Vanadium (V) 6.98 Zinc (Zn) 0.538 -
TABLE 6 EC2472A Aluminum Calcium Iron Nickel Zinc Bottle (ppm) Additive (ppm) (ppm) (ppm) (ppm) (ppm) 1 25 blank <0.150 14.5 3.96 0.238 0.106 2 25 1000 ppm 17.1 17 98 123 3.36 EC6779A 3 25 1000 ppm 18.6 34.3 109 22.4 14.9 EC6818A 4 25 1000 ppm 14.4 16.9 46.9 7.56 0.524 EC2111A 5 25 1000 ppm 14.4 16.9 46.9 7.56 0.524 EC2483A 6 25 blank 1.03 13.2 7.19 0.951 0.473 - The percent iron removal to the resolved water is shown in
FIG. 7 . EC6818A demonstrated the strongest performance under these conditions. EC2111A and EC2483A did not show competitive performance to the two formulations containing the peroxyacid. The same observation is observed with regards to Zn and Ni removal. - Example 3 testing was repeated under the same conditions to analyze increased dosages of the chemistries and the effect of R-3461 on EC6818A and EC6779A performance. The experimental design and concentration of metals found in the resolved water is shown in Table 7.
-
TABLE 7 Aluminum Iron Nickel Zinc Additive (ppm) (ppm) (ppm) (ppm) 2500 ppm EC2111A 20.8 27.5 8.23 2.93 2500 ppm EC2483A 4.9 34.8 1.15 0.567 blank 3.3 11.9 0.765 0.347 2500 ppm EC6779A 15.6 111 66.5 3.39 5000 ppm EC6779A 48.7 99.2 170 8.61 2500 ppm EC6779A 4.07 100 77.8 2.77 with 2500 ppm R-3461 2500 ppm EC6818A 5.28 95 214 6.52 5000 ppm EC6818A 7.1 83.8 304 5.36 2500 ppm EC6818A 4.24 80.6 105 3.85 with 2500 ppm R-3461 blank 3.27 17.6 26.8 2 - Additional data regarding performance is shown in Table 8.
-
TABLE 8 Aluminum Iron Nickel Zinc Additive (Al) (Fe) (Ni) (Zn) 2500 ppm EC2111A 449 12 25 61 2500 ppm EC2483A 106 16 3 12 blank 71 5 2 7 2500 ppm EC6779A 337 50 200 70 5000 ppm EC6779A 1051 45 511 178 2500 ppm EC6779A 88 45 234 57 with 2500 ppm R-3461 2500 ppm EC6818A 114 43 643 135 5000 ppm EC6818A 153 38 913 111 2500 ppm EC6818A 91 37 315 80 with 2500 ppm R-3461 blank 71 8 80 41 - The percent metals removal is substantially higher than expected based on the ICP analysis of the crude oil. In addition, the blanks show considerably different values for Zn and Ni suggesting the homogeneity of the crude oil sample may be of concern. R-3461A did not boost the peroxyacid formulations' performances demonstrating that the use of sodium gluconate is not required in combination with the peroxyacid compositions. However, again, the two peroxyacid formulations outperformed the carboxylic acids EC2111A (acetic acid) and EC2483A (malic acid) as shown in
FIG. 8 . - Filterable solids analysis on the top oil fraction of the resolved emulsion this testing is shown in
FIG. 9 and suggest that solids removal has been effective relative to the blanks with the peroxyacid formulations. - Bottle Testing methodology was used to assess efficacy of various metal removal agents. Characterization of the emulsion band formed while processing this slate found 9300 ppm Fe, suggesting the Fe may play a role in emulsion stabilization. The crude oil (treated at the refinery with emulsion breaker) was homogenized and then 90 mL aliquots were transferred into five medicine bottles containing 10 mL of distilled water each. Three of the bottles were charged with one of the following metal removal agents at 1000 ppm: EC2111A, EC6779A or CORR11540A. The samples were emulsified using 100% shear and transferred to a heating block set to 120 ° C. The emulsions were then shocked with 4000 V for 20 minutes to facilitate complete emulsion resolution. The samples were then cooled to ambient temperature. The resolved water phases were collected for analysis by ICP and the results are shown in Table 9. CORR11540A, a solution of R-3461 with a surfactant, did not show performance relative to EC2111A and EC6779A. This suggests again that the chelant is not effective in the absence of an acid.
-
TABLE 9 Aluminum (Al) Iron (Fe) Nickel (Ni) Zinc (Zn) Treatment (ppm) (ppm) (ppm) (ppm) Blank 1<0.75 <0.12 1.13 <0.25 EC2111A 7.72 3.55 14.8 1.66 (1000 ppm) EC6779A 9.86 1.51 7.67 0.39 (1000 ppm) CORR11540A <0.75 0.97 2.02 <0.25 (1000 ppm) Blank 2 <0.75 0.33 0.46 <0.25 - The ability of peroxyacetic acid to remove metals from slop oil was analyzed. A sample of slop oil was received in the form of a stable emulsion. The emulsion does not resolve after prolonged periods of quiescent settling in the absence of chemical treatment. The sample received was homogenized and sampled into 100 mL aliquots. One aliquot each was treated with 1000 ppm of EC2483A or EC6779A. After 48 hours all the samples contained emulsion except those treated with EC6779A.
- The ability of peroxyacetic acid to remove metals from slop oil (as a stable emulsion) was further analyzed. The emulsion does not resolve after prolonged periods of quiescent settling in the absence of chemical treatment. The sample received was homogenized and sampled into 100 mL aliquots. One aliquot each was treated with 1000 or 5000 ppm of EC2111A (acetic acid) or EC6779A (peracetic acid). The treated emulsions were stored for 24 hours. The two samples treated with EC6779A contained 1% resolved water. The samples were then centrifuged at 140° C. for 30 minutes. Pictures of the resulting resolved emulsion are provided in
FIG. 10 . The EC6779A samples contained yellow water and significantly more oil free solids were observed at the bottom of the tubes. ICP analysis on the top oil fraction and the resolved water phase are given in Table 10. -
TABLE 10 Al Ca Fe Ni V Zn Water Analysis (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) pH@25° C. 5000 ppm EC6779A 29.3 676 281 2.06 4.76 81.8 3 1000 ppm EC6779A 9.22 738 175 0.727 0.431 26.5 3 5000 ppm EC2111A 70.5 702 191 0.182 0.57 0.946 3 1000 ppm EC2111A 18.9 738 159 0.175 0.156 1.53 3 Karl Hydrocarbon Al Ca Fe Ni V Zn Fischer Skimmings (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) Water 5000 ppm EC6779A 101 122 288 32.8 98.6 21 0.34 1000 ppm EC6779A 73.6 60.9 249 36..8 114 23.2 0.48 5000 ppm EC2111A 16.4 7.42 45.6 39.4 120 7.71 0.35 1000 ppm EC2111A 26.4 23.1 70.8 38.2 119 9.43 0.1 Slop oil without treatment 234 534 686 15 44.1 66.1 % Removal of Metals Al Ca Fe Ni V Zn to the Water Phase (%) (%) (%) (%) (%) (%) 5000 ppm EC6779A 56 149 83 15 44 44 1000 ppm EC6779A 35 150 181 16 49 21 5000 ppm EC2111A 37 133 101 17 52 4 1000 ppm EC2111A 19 143 98 16 51 5 - A gallon of a light crude oil from the Gulf Coast was collected for ICP analysis. An aliquot of this crude oil found 25 ppm Fe, 4 ppm Ni, and 1 ppm Zn. The crude oil was homogenized and then 90 mL aliquots were transferred into eight medicine bottles containing 10 mL of distilled water each. The bottles were all charged with 25 ppm EC2472A and the metal removal agents as outlined in Table 11.
-
TABLE 11 Filterable Solids on Top Bottle Additive Oil Fraction (ppm) 1 blank 1768 2 1000 ppm EC6779A NA 3 1000 ppm EC6818A 1210 4 1000 ppm EC2111A 1800 5 1000 ppm EC2483A 1833 6 blank 2008 7 2500 ppm EC2111A 1490 8 2500 ppm EC2483A 2008 9 blank 1755 10 2500 ppm EC6779A 1396 11 5000 ppm EC6779A 1152 12 2500 ppm EC6779A with 2500 ppm 2071 R-3461 13 2500 ppm EC6818A 1501 14 5000 ppm EC6818A 1588 15 2500 ppm EC6818A with R-3461 1872 16 blank 976 - The samples were emulsified using 80% shear and transferred to a heating block set to 120° C. The emulsions were then shocked with 3000 V for 20 minutes to facilitate complete emulsion resolution. The samples were then cooled to ambient temperature. The top oil fraction was sampled for filterable solids (right column of Table 11) and the resolved water phases were collected for analysis by ICP (Table 12).
-
TABLE 12 Aluminum Iron Nickel Zinc Bottle Additive (ppm) (ppm) (ppm) (ppm) 1 blank <0.150 3.96 0.238 0.106 2 1000 ppm EC6779A 17.1 98 123 3.36 3 1000 ppm EC6818A 18.6 109 22.4 14.9 4 1000 ppm EC2111A 14.4 46.9 7.56 0.524 5 1000 ppm EC2483A 14.4 46.9 7.56 0.524 6 blank 1.03 7.19 0.951 0.473 7 2500 ppm EC2111A 20.8 27.5 8.23 2.93 8 2500 ppm EC2483A 4.9 34.8 1.15 0.567 9 blank 3.3 11.9 0.765 0.347 10 2500 ppm EC6779A 15.6 111 66.5 3.39 11 5000 ppm EC6779A 48.7 99.2 170 8.61 12 2500 ppm EC6779A 4.07 100 77.8 2.77 with 2500 ppm R-3461 13 2500 ppm EC6818A 5.28 95 214 6.52 14 5000 ppm EC6818A 7.1 83.8 304 5.36 15 2500 ppm EC6818A 4.24 80.6 105 3.85 with 2500 ppm R-3461 16 blank 3.27 17.6 26.8 2
% Removal of Ni, Fe, Al and Zn is given in Table 13 and was approximated using the total metals analysis on the raw crude sample. R-3461 did not promote metals removal when coupled with the peroxyacids. EC6779A and EC6818A outperformed EC2111A and EC2483A. It is unclear which peroxyacid formulation is more effective based on this testing. -
TABLE 13 % Migration from the Hydrocarbon Phase Aluminum Iron Nickel Zinc Bottle Additive (Al) (Fe) (Ni) (Zn) 1 blank 2 1 2 2 1000 ppm EC6779A 369 44 369 69 3 1000 ppm EC6818A 401 49 67 308 4 1000 ppm EC2111A 311 21 23 11 5 1000 ppm EC2483A 311 21 23 11 6 blank 22 3 3 10 7 2500 ppm EC2111A 449 12 25 61 8 2500 ppm EC2483A 106 16 3 12 9 blank 71 5 2 7 10 2500 ppm EC6779A 337 50 200 70 11 5000 ppm EC6779A 1051 45 511 178 12 2500 ppm EC6779A 88 45 234 57 with 2500 ppm R-3461 13 2500 ppm EC6818A 114 43 643 135 14 5000 ppm EC6818A 153 38 913 111 15 2500 ppm EC6818A 91 37 315 80 with 2500 ppm R-3461 16 blank 71 8 80 41 - The inventions being thus described, it will be obvious that the same may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the inventions and all such modifications are intended to be included within the scope of the following claims. The above specification provides a description of the manufacture and use of the disclosed compositions and methods. Since many embodiments can be made without departing from the spirit and scope of the invention, the invention resides in the claims. The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilized for realizing the invention in diverse forms thereof.
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WO2022094560A1 (en) * | 2020-10-29 | 2022-05-05 | Marathon Petroleum Company Lp | Systems and methods for separating water and removing solids from pre-treated and unfiltered feedstock |
WO2022094580A1 (en) * | 2020-10-29 | 2022-05-05 | Marathon Petroleum Company Lp | Systems and methods for enhanced inorganic contaminant removal from hydrocarbon feedstock |
US11352570B1 (en) | 2020-10-29 | 2022-06-07 | Marathon Petroleum Company Lp | Systems and methods for enhanced inorganic contaminant removal from hydrocarbon feedstock |
US11702601B2 (en) | 2020-10-29 | 2023-07-18 | Marathon Petroleum Company Lp | Systems and methods for separating water and removing solids from pre-treated and unfiltered feedstock |
US11725151B2 (en) | 2020-10-29 | 2023-08-15 | Marathon Petroleum Company Lp | Systems and methods for enhanced inorganic contaminant removal from hydrocarbon feedstock |
US11788023B2 (en) | 2021-10-12 | 2023-10-17 | Marathon Petroleum Company Lp | Systems and methods of converting renewable feedstocks into intermediate hydrocarbon blend stocks and transportation fuels |
Also Published As
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KR102586688B1 (en) | 2023-10-06 |
KR20210082515A (en) | 2021-07-05 |
SG11202105464XA (en) | 2021-06-29 |
CA3121514C (en) | 2023-05-02 |
WO2020117724A1 (en) | 2020-06-11 |
EP3867336A1 (en) | 2021-08-25 |
CA3121514A1 (en) | 2020-06-11 |
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