CN107438601A - 开发用于去除硫化氢的新颖的高温稳定清除剂 - Google Patents
开发用于去除硫化氢的新颖的高温稳定清除剂 Download PDFInfo
- Publication number
- CN107438601A CN107438601A CN201680018141.3A CN201680018141A CN107438601A CN 107438601 A CN107438601 A CN 107438601A CN 201680018141 A CN201680018141 A CN 201680018141A CN 107438601 A CN107438601 A CN 107438601A
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- China
- Prior art keywords
- hydrogen sulfide
- composition
- alkyl
- ring structure
- group
- Prior art date
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 74
- 239000002516 radical scavenger Substances 0.000 title claims description 61
- 239000000203 mixture Substances 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 51
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010779 crude oil Substances 0.000 claims abstract description 10
- 239000003245 coal Chemical class 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 150000001412 amines Chemical class 0.000 claims description 28
- 229910052760 oxygen Inorganic materials 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 21
- 239000005864 Sulphur Substances 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 17
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 125000000304 alkynyl group Chemical group 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003139 biocide Substances 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 125000002355 alkine group Chemical group 0.000 claims description 5
- 230000003115 biocidal effect Effects 0.000 claims description 5
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 239000003345 natural gas Substances 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000002455 scale inhibitor Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 125000002009 alkene group Chemical group 0.000 claims description 4
- 239000003995 emulsifying agent Substances 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- NMJORVOYSJLJGU-UHFFFAOYSA-N methane clathrate Chemical compound C.C.C.C.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O NMJORVOYSJLJGU-UHFFFAOYSA-N 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920001131 Pulp (paper) Polymers 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000002551 biofuel Substances 0.000 claims description 2
- 238000005065 mining Methods 0.000 claims description 2
- 239000006025 fining agent Substances 0.000 claims 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 43
- -1 Alkyl aryl sulphonic acid Chemical compound 0.000 description 36
- 239000012530 fluid Substances 0.000 description 28
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 19
- 239000002253 acid Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- 239000000523 sample Substances 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000098 polyolefin Polymers 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 5
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical class OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000010452 phosphate Chemical group 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 241000894007 species Species 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006324 polyoxymethylene Polymers 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004155 Chlorine dioxide Substances 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000001469 hydantoins Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- YRIZYWQGELRKNT-UHFFFAOYSA-N 1,3,5-trichloro-1,3,5-triazinane-2,4,6-trione Chemical compound ClN1C(=O)N(Cl)C(=O)N(Cl)C1=O YRIZYWQGELRKNT-UHFFFAOYSA-N 0.000 description 1
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- 239000001384 succinic acid Substances 0.000 description 1
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229950009390 symclosene Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本公开提供适用于去除硫化氢和硫醇、降低硫化氢和硫醇的量或以其它方式控制硫化氢和硫醇的组合物和方法。所述组合物和方法可以用于如当处理原油类、天然气类和/或煤炭类产品时硫化氢造成问题的任何工业中。本公开提供可以减少各种介质中的硫化氢的量或消除各种介质中的硫化氢的组合物和方法。
Description
相关申请的交叉引用
本申请要求2015年4月22日提交的美国专利申请序列号62/151,083的优先权,其公开内容以全文引用的方式并入本文中。
背景技术
1.发明领域
本公开大体上涉及液体和气态流中的污染物的去除。更确切地说,本发明涉及液体和气态流的硫化氢清除剂。
2.相关技术说明
硫化氢的毒性极大并且在油气工业中造成难题。硫化氢从液体或气态烃流中的去除也是一个造成某些安全性风险的问题。与硫化氢相关的许多问题存在于原油和与原油相关的废水的钻探、生产、运输、储存以及加工中。在生产天然气期间产生类似的问题。
含硫化合物的存在可能导致含硫盐沉积,其可以造成输送管道、阀门、调节器等的堵塞和腐蚀。即使燃烧的天然气也需要经过处理以避免引起SO2形成的酸雨。此外,在制造气体工业或焦炭制备工业中,含有不可接受含量的硫化氢的煤气通常由烟煤的干馏产生。
由于硫化氢具有攻击性臭味并且含有硫化氢的天然气被称作“酸”气,因此针对较低硫化氢含量的处理一般称作“脱硫”处理。
发明内容
本公开的某些方面涉及用于处置硫化氢的组合物和方法。在一个实施例中,公开一种处理流中的硫化氢的方法。所述方法包含向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中C1-C6环结构可以是芳香族或环状脂肪族的;
C1-C6可以独立地选自碳、氮、氧以及硫,其中C2可以存在或不存在,并且如果不存在,那么环结构是五元环结构;
其中环结构可以被拉电子基团或供电子基团取代;
X可以选自由以下组成的组:碳、氮、氧、硫、羰基、烷基以及烯基;
R可以选自由以下组成的组:氢、烷基、烯基、炔基、氮以及氧,其中烷基、烯基以及炔基可以未被取代或被取代;
k是选自0到25的整数;并且
m是选自1到4的整数。
在另一个实施例中,公开一种处理流中的硫化氢的方法。所述方法包含向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中C1-C6环结构可以是芳香族或环状脂肪族的;C1-C6可以独立地选自碳、氮、氧以及硫,其中C2可以存在或不存在,并且如果不存在,那么环结构是五元环结构;其中环结构可以被拉电子基团或供电子基团取代;X可以选自由以下组成的组:N(NH)、(NCH2OH)以及O;R可以选自由以下组成的组:C2-C8直链或分支链烷基、C2-C8直链或分支链烯基以及C2-C8直链或分支链炔基;Y是氮或氧;k是选自0到25的整数;并且m是选自1到4的整数。
在又一个实施例中,公开一种处理流中的硫化氢的方法。所述方法包含向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中每一个C1-C6环结构可以是芳香族或环状脂肪族的;
C1-C6可以独立地选自碳、氮、氧以及硫,其中C6可以存在或不存在,并且如果不存在,那么环结构是五元环结构;其中环结构可以被拉电子基团或供电子基团取代;
每一个X独立地选自由以下组成的组:N、NH以及O;每一个R独立地选自由以下组成的组:O、C1-C8直链或分支链烷基、C1-C8直链或分支链烯基以及C1-C8直链或分支链炔基;每一个k是选自0到25的整数;并且每一个m是选自1到4的整数。
在另一个实施例中,公开一种处理流中的硫化氢的方法。所述方法包含向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中C1-C6独立地选自由以下组成的组:碳、氮、氧以及硫;R1-R6独立地选自由以下组成的组:氢、X-(CH2)n-Y-(CH2O)n-H以及X选自由以下组成的组:碳、氮、氧以及硫;Y选自由以下组成的组:氮、氧以及硫;并且n是在0-6范围内的数目。
在另一个实施例中,公开一种处理流中的硫化氢的方法。所述方法包含向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中“x”是任何数目,或0与约25之间的数目的任何范围,如约1到约5、约6到约15或约16到约25。尽管第二含氮取代基显示于对位中,但其还可以位于邻位和/或间位中。
前文已相当宽泛地概述了本公开的特征和技术优势,使得可以更好地理解下文的具体实施方式。在下文中将描述本发明的额外特征和优势,所述额外特征和优势形成本申请的权利要求的主题。所属领域的技术人员应了解,所公开的概念和具体实施例可易于用作修改或设计用于实现本公开的相同目的的其它实施例的基础。所属领域的技术人员还应意识到,这类同等实施例不脱离如在所附权利要求书中所阐述的本公开的精神和范围。
附图说明
下文具体参考图式描述了具体实施方式,其中:
图1显示接收自一种当前公开的清除剂的热解重量分析的数据。
具体实施方式
下文描述各种实施例。可以参照以下具体实施方式更好地理解实施例的各个要素的关系和功能。然而,实施例不限于下文明确描述的那些实施例。应指出,在某些例子中,可能已经省略了对理解本文所公开的实施例不必要的细节,如常规制造和组装。
本公开提供适用于去除硫化氢和硫醇、降低硫化氢和硫醇的量或以其它方式控制硫化氢和硫醇的组合物和方法。所述组合物和方法可以用于如当处理原油类、天然气类和/或煤炭类产品时硫化氢造成问题的任何工业中。本公开提供可以减少各种介质中的硫化氢的量或消除各种介质中的硫化氢的组合物和方法。在下文中,应理解,与短语例如“处理硫化氢”有关的术语“处理”将解释为意指去除、降低、减少和/或消除硫化氢。
举例来说,在一个方面中,处理硫化氢的方法可以涵盖从烃流中完全消除硫化氢。在另一个方面中,处理硫化氢的方法可以涵盖减少或降低烃流中的硫化氢含量。
在一些实施例中,本公开涉及能够处理硫化氢的化学组合物。这类组合物一般可以被称作清除剂。清除剂可以有效地处理任何环境中的液体或气态流中的硫化氢。在一些实施例中,清除剂是无水的。无水清除剂可以与非水性溶剂如烃溶剂掺合,以产生可以用于任何环境或气候中的组合物。无水组合物可以任选地与用于非水性应用的亲水性溶剂(例如醇、二醇、多元醇)掺合。或者,组合物可以与直接用于水性应用中的水相掺合。在一些实施例中,清除剂可以是油溶性的。在一些实施例中,组合物排除三嗪化合物。在某些实施例中,组合物不生成不可控制的乳液,意指其对所产生的流体的油/水分离和水质不具有负面影响。此外,在某些方面中,当前公开的分子可以用作腐蚀抑制剂和/或结垢抑制剂。
在一些实施例中,组合物包含具有以下通式的一种或多种清除剂化合物:
六元环可以是芳香族或环状脂肪族的。在一些实施例中,环可以仅包括C1-C5,使得环是五元环。C1-C6可以独立地选自碳、氮、氧以及硫。C2-C4可以独立地选自基团:X-R-{(OCH2)kOH}m。不论环是否为五元环或六元环,其可以被拉电子基团取代,所述拉电子基团如CHO、CN、COOH、C(O)R1(其中R1可以是例如烷基)、NO2、Cl、I等;和/或其可以被供电子基团取代,所述供电子基团如胺、被取代的胺、醇、醚、烷基、苯基、烯基、烯基酰胺基等。“X”可以选自碳、氮、氧、硫、羰基、烷基以及烯基。“R”可以选自氢、烷基、烯基、炔基、氮或氧,未被取代或被一个或多个合适的取代基取代。“k”是选自0到25的整数并且m是选自1到4的整数。
在一些实施例中,六元环是芳香族环,X=N(NH),R=C1-C8烷基,并且k+m=18。在至少一个实施例中,六元环是芳香族的,X=NCH2OH,R=C1-C8烷基,并且k+m=7。在其它实施例中,清除剂化合物包含式:
其中六元环(或在一些实施例中,五元环)是芳香族或非环状的,并且M1-M3在环的邻位、对位或间位独立地选自直链或分支链烷基、烯基、炔基、CHO、CN、COOH、C(O)R1(其中R1可以是例如烷基)、NO2、Cl、I、胺、被取代的胺、醇、醚、烷基、苯基、烯基以及烯基酰胺基,X=N,并且R=CO或直链或分支链C1-C8烷基、烯基或炔基。C1-C6可以独立地选自碳、氮、氧以及硫,“k”是选自0到25的整数,并且m是选自1到4的整数。
在其它实施例中,清除剂化合物包含以下通式:
其中C1-C6环结构可以是芳香族或非环状的,X=N(NH)、(NCH2OH)或O,R=C2-C8烷基、烯基或炔基,其可以是分支链或直链的,并且Y=N或O。在一些实施例中,环可以仅包括C1-C5,使得环是五元环。C1-C6可以独立地选自碳、氮、氧以及硫。不论环是否为五元环或六元环,其可以被拉电子基团取代,所述拉电子基团如CHO、CN、COOH、C(O)R1(其中R1可以是例如烷基)、NO2、Cl、I等;和/或其可以被供电子基团取代,所述供电子基团如胺、被取代的胺、醇、醚、烷基、苯基、烯基、烯基酰胺基等,“k”是选自0到25的整数,并且m是选自1到4的整数。
在其它实施例中,清除剂化合物可以包含以下通用结构:
其中每一个C1-C6环结构可以是芳香族或非环状的,每一个X独立地选自N、NH或O,并且每一个R独立地选自O或可以是分支链或直链的C1-C8烷基、烯基或炔基。C1-C6可以独立地选自碳、氮、氧以及硫,“k”是选自0到25的整数,并且m是选自1到4的整数。在一些实施例中,环中的一个或两个可以仅包括C1-C5,使得环是五元环。不论环是否为五元环或六元环,其可以被拉电子基团取代,所述拉电子基团如CHO、CN、COOH、C(O)R1(其中R1可以是例如烷基)、NO2、Cl、I等;和/或其可以被供电子基团取代,所述供电子基团如胺、被取代的胺、醇、醚、烷基、苯基、烯基、烯基酰胺基等。
在一些实施例中,组合物包含一种或多种具有以下通式的清除剂:
C1-C6=C、N、O或S
C1-C6=CH2、CH
R1-R6=
尽管6元环在上文显示为非芳香族的,但在一些实施例中,其可以是芳香族的意指其包含三个双键。与是芳香族的相反,6元环还可以包含例如一个或两个双键。此外,在上文结构中,R1到R6中的任一个可以是氢。同样,R1到R6中的多于一个可以是氢。举例来说,R1到R5可以是氢。此外,清除剂化合物可以包括上文通用结构的二聚体和/或三聚体。
在一些实施例中,清除剂化合物选自由以下组成的组:
R=甲基、乙基、丙基、丁基 其中X=1-6
除其它半甲缩醛化合物以外,组合物可以包括前述清除剂化合物中的任一种或前述清除剂化合物的任何组合。在前述化合物中,“EWG”表示拉电子基团。可以使用任何拉电子基团,如CHO、CN以及C(O)CH3。在一些实施例中,组合物可以按各种比率包括任何数目的上文提到的结构。举例来说,组合物可以按约30:20:20的比率包括任三个上文提到的结构。组合物还可以包括任一种本文所公开的溶剂。
在某些实施例中,当前公开的清除剂化合物可以通过使环脂肪族胺与甲醛溶液或多聚甲醛反应来制造。在其它实施例中,这些化合物可以通过如下方式制造:例如使环脂肪族胺与环氧乙烷(EO)、环氧丙烷(PO)和/或缩水甘油反应以产生反应产物,并且随后使反应产物与多聚甲醛或甲醛溶液(例如,福尔马林)反应。
在一些实施例中,将包含一种或多种清除剂化合物的组合物以纯(或活性)方式添加到液体或气态流中,意指组合物不包含溶剂或组合物主要由一种或多种清除剂组成,意指其排除溶剂。在其它实施例中,组合物可以包含溶剂。在一些实施例中,溶剂包括异丙醇、甲醇、甲苯、水、二甲苯、乙二醇以及丙二醇中的一种或多种。在一些实施例中,溶剂包含约50重量%的一种或多种清除剂化合物,但在其它实施例中,溶剂可以包含约10重量%到约99重量%、如约30重量%到约70重量%的一种或多种清除剂化合物。
这些清除剂在约150℃到约200℃范围内的高温下热稳定并且其即使在这些高温下也维持其硫化氢清除能力。这些清除剂也具有低结垢可能性,含有低量的氮或完全没有氮,并且无腐蚀性。在一些方面,当前公开的清除剂可以用作腐蚀抑制剂。
在一个实施例中,本公开的组合物包含以下清除剂:
其中“k”=1-10。
前述清除剂可以根据以下合成方案制造,其中C1-C6、X、R、k以及m如上文所定义,并且n=1-100:
一般来说,N-苯基二乙醇胺或以下段落中所公开的任一种胺可以与约1-3摩尔的多聚甲醛(或含有约10%到约90%的甲醛于水中的甲醛溶液)反应以制造根据本公开的清除剂。在一些实施例中,胺可以与约1摩尔到约3摩尔的多聚甲醛反应以制造清除剂。
在一个实施例中,可以在约70℃下熔融约1到约2摩尔的固体N-苯基二乙醇胺以获得液体。可以将液体添加到配备有磁性搅拌器、氮气入口以及温度探针的反应烧瓶中。可以施加热以将内含物加热到约80℃。可以贯穿整个反应扫除反应混合物上方的氮气。随后可以将约0.001到约0.035摩尔的氢氧化钾(KOH)溶液添加到反应烧瓶中,并且可以在80℃下搅拌反应物约20分钟。随后可以使用例如固体加料漏斗将约1到约2摩尔的固体多聚甲醛球粒分批添加到反应混合物中。在一些实施例中,多聚甲醛以每10分钟约5到10克的速率添加。已经添加所有多聚甲醛后,可以在80℃下将反应混合物加热约2到4小时以制造所期望的清除剂化合物。在这个特定实施例中,清除剂的pH是约7.6并且75℉下的粘度是约2000。
虽然在上文合成方案中将N-苯基二乙醇胺描绘为起始物质,但起始物质不限于这种胺并且可以使用许多其它胺。合适胺的说明性、非限制性实例包括(但不限于)苯胺、被取代的苯胺、环己胺、芳香族烷醇胺以及环脂肪族烷醇胺。
可以使用前述胺中的任一种并且可以使用这些胺的乙氧基化衍生物、丙氧基化衍生物和/或烷氧基化衍生物中的任一种。同样,N-苯基二乙醇胺可以与环氧乙烷、环氧丙烷、缩水甘油或环氧化物反应。
本公开的组合物包括如本文所定义的一种或多种清除剂。组合物还可以任选地包括一种或多种添加剂。合适的添加剂包括(但不限于)沥青烯抑制剂、石蜡抑制剂、腐蚀抑制剂、结垢抑制剂、乳化剂、水澄清剂、分散剂、破乳剂、额外硫化氢清除剂、气体水合物抑制剂、杀生物剂、pH调节剂、表面活性剂、溶剂以及其任何组合。
合适的沥青烯抑制剂包括(但不限于)脂肪族磺酸;烷基芳基磺酸;芳基磺酸盐;木质素磺酸盐;烷基酚/醛树脂和类似磺化树脂;聚烯烃酯;聚烯烃酰亚胺;具有烷基、亚烷基苯基或亚烷基吡啶基官能团的聚烯烃酯;聚烯烃酰胺;具有烷基、亚烷基苯基或亚烷基吡啶基官能团的聚烯烃酰胺;具有烷基、亚烷基苯基或亚烷基吡啶基官能团的聚烯烃酰亚胺;烯基/乙烯基吡咯烷酮共聚物;聚烯烃与马来酸酐或乙烯基咪唑的接枝聚合物;超枝聚酯酰胺;聚烷氧基化沥青烯;两性脂肪酸;丁二酸烷基酯的盐、脱水山梨糖醇单油酸酯;聚异丁烯丁二酸酐;以及其任何组合。
合适的石蜡抑制剂包括(但不限于)石蜡晶体调节剂和分散剂/晶体改性剂组合。合适的石蜡晶体调节剂包括(但不限于)丙烯酸烷基酯共聚物、丙烯酸烷基酯乙烯基吡啶共聚物、乙烯乙酸乙烯酯共聚物、马来酸酐酯共聚物、分枝聚乙烯、萘、蒽、微晶蜡和/或沥青烯以及其组合。合适的分散剂包括(但不限于)十二烷基苯磺酸盐、烷氧基化烷基酚、烷氧基化烷基酚树脂以及其任何组合。
合适的腐蚀抑制剂包括(但不限于)酰氨基胺、季胺、酰胺、磷酸酯以及其任何组合。
合适的结垢抑制剂包括(但不限于)磷酸盐、磷酸酯、磷酸、膦酸盐、膦酸、聚丙烯酰胺、丙烯酰氨基-甲基丙烷磺酸酯/丙烯酸共聚物(AMPS/AA)的盐、亚膦酸化马来酸共聚物(PHOS/MA)、聚马来酸/丙烯酸/丙烯酰氨基-甲基丙烷磺酸酯三元共聚物(PMA/AMPS)的盐以及其任何组合。
合适的乳化剂包括(但不限于)羧酸盐、羧酸或羧酸酐与胺之间的酰化反应的产物、糖的烷基、酰基和酰胺衍生物(烷基-糖乳化剂)以及其任何组合。
合适的水澄清剂包括(但不限于)无机金属盐,如矾、氯化铝以及氢氯酸铝;或有机聚合物,如丙烯酸类聚合物、丙烯酰胺类聚合物、聚合胺、烷醇胺、硫代氨基甲酸酯;阳离子聚合物,如氯化二烯丙基二甲基铵(DADMAC);以及其任何组合。
合适的分散剂包括(但不限于)具有2-50个碳的脂肪族膦酸,如羟基乙基二膦酸,和氨基烷基膦酸,例如具有2-10个N原子的聚氨基亚甲基膦酸盐,例如各自带有至少一个亚甲基膦酸基团;后者的实例是乙二胺四(亚甲基膦酸盐)、二亚乙基三胺五(亚甲基膦酸盐)以及在每一个N原子之间具有2-4个亚甲基的三胺聚亚甲基膦酸盐和四胺聚亚甲基膦酸盐,每一膦酸盐中的亚甲基数目中的至少2个不同。其它合适的分散剂包括木质素或木质素衍生物(如木质素磺酸盐)和萘磺酸和衍生物,以及其任何组合。
合适的破乳剂包括(但不限于)十二烷基苯甲基磺酸(DDBSA);二甲苯磺酸(NAXSA)的钠盐;环氧化化合物和丙氧基化化合物;阴离子阳离子和非离子表面活性剂;树脂,如酚类树脂和环氧树脂;以及其任何组合。
合适的额外硫化氢清除剂包括(但不限于)氧化剂(例如无机过氧化物,如过氧化钠或二氧化氯)、醛(例如具有1-10个碳,如甲醛或戊二醛或(甲基)丙烯醛)、三嗪(例如单乙醇胺三嗪、单甲胺三嗪以及来自多种胺或其混合物的三嗪)、乙二醛以及其任何组合。
合适的气体水合物抑制剂包括(但不限于)热力学水合物抑制剂(THI)、动力学水合物抑制剂(KHI)、抗聚结物(AA)以及其任何组合。合适的热力学水合物抑制剂包括(但不限于)NaCl盐、KCl盐、CaCl2盐、MgCl2盐、NaBr2盐、甲酸盐(formate brine)(例如,甲酸钾)、多元醇(如葡萄糖、蔗糖、果糖、麦芽糖、乳糖、葡糖酸盐、单乙二醇、二乙二醇、三乙二醇、单丙二醇、二丙二醇、三丙二醇、四丙二醇、单丁二醇、二丁二醇、三丁二醇、甘油、二甘油、三甘油以及糖醇(例如,山梨糖醇、甘露糖醇))、甲醇、丙醇、乙醇、二醇醚(如二乙二醇单甲醚、乙二醇单丁醚)、醇的烷基或环状酯(如乳酸乙酯、乳酸丁酯、苯甲酸甲基乙酯)以及其任何组合。合适的动力学水合物抑制剂和抗聚结物包括(但不限于)聚合物和共聚物、多糖(如羟基-乙基纤维素(HEC)、羧甲基纤维素(CMC)、淀粉、淀粉衍生物以及黄原胶)、内酰胺(如聚乙烯己内酰胺、聚乙烯基内酰胺)、吡咯烷酮(如各种分子量的聚乙烯吡咯烷酮)、表面活性剂(如脂肪酸盐、乙氧基化醇、丙氧基化醇、脱水山梨糖醇酯、乙氧基化脱水山梨糖醇酯、脂肪酸的聚甘油酯、烷基葡糖苷、烷基聚葡糖苷、烷基硫酸盐、烷基磺酸盐、烷基酯磺酸盐、烷基芳香族磺酸盐、烷基甜菜碱、烷基酰氨基甜菜碱)、烃类分散剂(如木质素磺酸盐、亚氨基二丁二酸盐、聚天冬氨酸盐)、氨基酸、蛋白质以及其任何组合。
合适的杀生物剂包括(但不限于)氧化杀生物剂和非氧化杀生物剂。合适的非氧化杀生物剂包括例如醛(例如甲醛、戊二醛以及丙烯醛)、胺型化合物(例如季胺化合物和椰油二胺)、卤化化合物(例如溴硝丙二醇和2-2-二溴-3-氮基丙酰胺(DBNPA))、硫化合物(例如异噻唑酮、氨基甲酸酯以及甲硝哒唑)、季鏻盐(例如四(羟甲基)硫酸鏻(THPS))以及其组合。合适的氧化杀生物剂包括例如次氯酸钠、三氯异氰尿酸、二氯异氰尿酸、次氯酸钙、次氯酸锂、氯化乙内酰脲、稳定化次溴酸钠、活化溴化钠、溴化乙内酰脲、二氧化氯、臭氧、过氧化物以及其任何组合。
合适的pH调节剂包括(但不限于)碱金属氢氧化物、碱金属碳酸盐、低pH叔胺、碱金属碳酸氢盐、碱土金属氢氧化物、碱土金属碳酸盐、碱土金属碳酸氢盐以及其混合物或组合。示范性的pH调节剂包括NaOH、KOH、Ca(OH)2、CaO、Na2CO3、KHCO3、K2CO3、NaHCO3、MgO以及Mg(OH)2。
合适的表面活性剂包括(但不限于)阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂以及其组合。阴离子表面活性剂包括烷基芳基磺酸盐、烯烃磺酸盐、链烷烃磺酸盐、醇硫酸盐、醇醚硫酸盐、烷基羧酸盐和烷基醚羧酸盐,以及烷基和乙氧基化烷基磷酸酯,以及单烷基和二烷基磺化丁二酸盐和磺化琥珀酰胺酸盐以及其组合。阳离子表面活性剂包括烷基三甲基季铵盐、烷基二甲基苯甲基季铵盐、二烷基二甲基季铵盐、咪唑啉盐以及其组合。非离子表面活性剂包括醇烷氧基化物;烷基酚烷氧基化物;乙烯、丙烯和丁烯氧化物的嵌段共聚物;烷基二甲胺氧化物;烷基-双(2-羟乙基)胺氧化物;烷基酰胺丙基二甲胺氧化物;烷基酰胺丙基-双(2-羟乙基)胺氧化物;烷基聚葡糖苷;聚烷氧基化甘油酯;脱水山梨糖醇酯和聚烷氧基化脱水山梨糖醇酯;以及烷酰基聚乙二醇酯和二酯;以及其组合。也包括甜菜碱和磺基甜菜碱(sultane);两性表面活性剂,如烷基两性乙酸盐和两性二乙酸盐、烷基两性丙酸盐和两性二丙酸盐;烷基亚氨基二丙酸盐以及其组合。
在某些实施例中,表面活性剂可以是季铵化合物、胺氧化物、离子或非离子表面活性剂或其任何组合。合适的季胺化合物包括(但不限于)烷基苯甲基氯化铵、苯甲基椰油烷基(C12-C18)二甲基氯化铵、二椰油烷基(C12-C18)二甲基氯化铵、二牛脂二甲基氯化铵、二(氢化牛脂烷基)二甲基季铵甲基氯、甲基双(2-羟乙基椰油烷基(C12-C18)季铵氯化物、二甲基(2-乙基)牛脂铵甲基硫酸盐、正十二烷基苯甲基二甲基氯化铵、正十八烷基苯甲基二甲基氯化铵、正十二烷基三甲基硫酸铵、大豆烷基三甲基氯化铵以及氢化牛脂烷基(2-乙基己基)二甲基季铵甲基硫酸盐。
合适的溶剂包括(但不限于)水、异丙醇、甲醇、乙醇、2-乙基己醇、重质芳香族石脑油、甲苯、乙二醇、乙二醇单丁醚(EGMBE)、二乙二醇单乙醚、二甲苯以及其组合。适用于与组合物调配的代表性极性溶剂包括水、盐水、海水、醇(包括直链或分支链脂肪族醇,如甲醇、乙醇、丙醇、异丙醇、丁醇、2-乙基己醇、己醇、辛醇、癸醇、2-丁氧基乙醇等)、二醇和衍生物(乙二醇、1,2-丙二醇、1,3-丙二醇、乙二醇单丁醚等)、酮(环己酮、二异丁基酮)、N-甲基吡咯烷酮(NMP)、N,N-二甲基甲酰胺等等。适用于与组合物调配的非极性溶剂的代表包括脂肪族物,如戊烷、己烷、环己烷、甲基环己烷、庚烷、癸烷、十二烷、柴油等等;芳香族物,如甲苯、二甲苯、重质芳香族石脑油、脂肪酸衍生物(酸、酯、酰胺)等等。
在一些实施例中,溶剂是多羟基化溶剂、聚醚、醇或其组合。
在某些实施例中,溶剂是单乙二醇、甲醇、二甲亚砜(DMSO)、二甲基甲酰胺(DMF)、四氢呋喃(THF)或其组合。
在一些实施例中,本公开的组合物可以包含一种或多种清除剂、任选的一种或多种添加剂以及按组合物的重量计0到约80重量%的一种或多种溶剂。在某些实施例中,本公开的组合物可以包含按组合物的重量计0到约50重量%的一种或多种溶剂。在一些实施例中,组合物可以包含按组合物的重量计约20重量%到约50重量%的一种或多种溶剂,
当前公开的包含一种或多种硫化氢清除剂的组合物可以用以在其中期望处理硫化氢的任何工业应用中处理硫化氢。举例来说,当用原油类产品、天然气类产品和/或煤炭类产品工作时,硫化氢一般将造成某些问题并且当前公开的清除剂可以用以消除或显著缓解这类问题。
组合物可以用于使气体或液体(如酸气或酸液)脱硫。如本文所描述,组合物可以用于通过用有效量的包含清除剂的组合物处理所述流来从气体或液体流中清除硫化氢。组合物可以用于其中期望从气体或液体流中捕获硫化氢的任何工业中。在某些实施例中,组合物可以用于水系统、冷凝物/油系统/气体系统或其任何组合中。
在某些实施例中,组合物可以施用到原油或天然气的生产、运输、储存和/或分离中所制造或使用的气体或液体。在某些实施例中,组合物可以施用到燃煤工艺(如燃煤发电厂)中所使用或制造的气体流。在某些实施例中,组合物可以施用到废水工艺、农场、屠宰厂、土地填筑、市政当局废水厂、炼焦煤工艺、保健行业、害虫消除、采矿操作、纸浆和纸设施或生物燃料工艺中所制造或使用的气体或液体。
组合物可以添加到含有硫化氢的任何流体或气体或可以暴露于硫化氢的流体或气体中。可以引入组合物的流体可以是水性介质。水性介质可以包含水、气体和/或液体烃。引入组合物的流体可以是液体烃。液体烃可以是任何类型的液体烃,包括(但不限于)原油、重油、处理过的残油、沥青油、焦化油、焦化瓦斯油(coker gas oil)、流体催化裂化器进料、瓦斯油、石脑油、流体催化裂化浆液、柴油燃料、燃油、喷射燃料、汽油以及煤油。在某些实施例中,气体可以是酸气。在某些实施例中,流体或气体可以是精炼烃产品。
用本公开的组合物处理的流体或气体可以在任何所选择温度下,所述温度如环境温度、低于环境温度的温度或高于环境温度而升高的温度。在某些实施例中,流体(例如液体烃)或气体可以在约40℃到约250℃的温度下。在某些实施例中,流体或气体可以在-50℃到300℃的温度下。
引入组合物的流体或气体可以含于许多不同类型的设备中和/或暴露于其。举例来说,流体或气体可以含于将流体或气体从一个点输送到另一个点的设备(如油和/或气管道)中。在某些实施例中,设备可以是油和/或气精炼厂的一部分,如管道、分离容器、脱水单元或气体管线。流体可以含于用于油提取和/或生产的设备(如井口)中和/或暴露于其。设备可以是燃煤发电厂的一部分。设备可以是擦洗器(例如湿烟气脱硫器、喷雾干燥吸收器、干燥吸附剂注射器、喷雾塔、接触塔或泡罩塔(bubble tower)等等)。设备可以是货船(cargo vessel)、储存容器、储料槽或连接槽、容器或处理单元的管道。在某些实施例中,流体或气体可以含于水系统、冷凝物/油系统/气体系统或其任何组合中。
可以通过任何适当方法将组合物引入流体或气体中以确保清除剂贯穿流体或气体而分散。可以使用机械设备注射组合物,所述机械设备如化学注射泵、管道T形件、注射配件、雾化器、管(quill)等等。取决于应用和要求,可以在存在或不存在一种或多种额外极性或非极性溶剂下引入组合物。在某些实施例中,可以使用脐带管线(umbilical line)将组合物泵入油和/或气管道中。在一些实施例中,毛细管注射系统可以用以将组合物递送到所选择流体。在特定实施例中,可以将组合物引入液体中并且混合。组合物可以作为水性或非水性溶液、混合物或浆液注入气体流中。在一些实施例中,流体或气体可以穿过包含如本文所公开的组合物的吸收塔。
组合物可以施用到流体或气体以提供如下的清除剂浓度:约1百万分率(ppm)到约1,000,000ppm、约1百万分率(ppm)到约100,000ppm、约10ppm到约75,000ppm、约100ppm到约45,000ppm、约500ppm到约40,000ppm、约1,000ppm到约35,000ppm、约3,000ppm到约30,000ppm、约4,000ppm到约25,000ppm、约5,000ppm到约20,000ppm、约6,000ppm到约15,000ppm或约7,000ppm到约10,000ppm。
每一特定系统或应用具有其自身要求,并且因此包含清除剂的组合物可以按所属领域的技术人员可以选择的任何有效剂量施用,这取决于特定应用和与所述应用相关的相关因素。举例来说,真正的酸气(例如含有大量的硫化氢)可能需要更高的剂量率。在某些实施例中,组合物可以按相对于流体或气体中所存在的硫化氢等摩尔的量或更大量施用到流体或气体。
通过用本公开的组合物处理,流体或气体中的硫化氢可以减少任何量。处理后残余硫化氢的实际量可能取决于起始量而变化。在某些实施例中,硫化氢可以从流体或气体中完全消除或其可以减少到按液体介质的体积计约150体积ppm或更小的含量,如在蒸气相中所测量。
在一些实施例中,本公开的组合物可以溶于水相中,使得所捕获的硫基物种(例如,硫化氢)将迁入水相中。如果存在乳液,那么所捕获的硫基物种可以从烃相(例如原油)迁入水相中并且与水相一起去除。如果不存在乳液,那么可以添加水洗液以吸引所捕获的硫基物种。在某些实施例中,可以在脱盐器中处理烃(例如原油)之前添加组合物,所述脱盐器使用水洗液使烃介质乳化以萃取水溶性污染物并且从烃分离并去除水相。
任选地,可以添加反乳化剂以有助于将水与烃分离。在某些实施例中,反乳化剂包括(但不限于)烷氧基化有机化合物、阴离子表面活性剂、非离子表面活性剂或这些物质的混合物。烷氧基化有机化合物包括(但不限于)酚醛树脂乙氧基化物和烷氧基化多元醇。阴离子表面活性剂包括烷基或芳基磺酸盐,如十二烷基苯磺酸钠盐。这些反乳化剂可以按接触按烃的重量计约1到约1000重量ppm的水的量添加。
实例
以下实例展现某些当前公开的清除剂的硫化氢清除能力。
包含清除剂的组合物:
通过测量蒸气相中的硫化氢减少来评估其性能。评估基于ASTMD5705测试方法的最佳化型式并且经设计用于确定蒸气相中的硫化氢减少。程序允许通过在受控制环境中使用气体检测管从酸流体的样品测量蒸气相中的硫化氢。
将H2S清除剂(其中“k”=1)的样品置于酸介质中并且使其在加热混合状态下反应特定的时长。流体介质包含50:50的粗:合成盐水。合成盐水包含低TDS和高TDS组成。低TDS可以包含0到约10,000并且高TDS可以包含大于约10,000到约20,000。用硫化氢净化流体介质来表示酸介质。剂量涉及液体中所测量的清除剂ppm与H2S ppm的比率。施用20:1和30:1的传统的全井内液流剂量。在清除剂剂量之前(空白)和之后在蒸气相中测量硫化氢。评估纯/活性(无溶剂)样品和热暴露样品的性能。在200℃下将H2S清除剂样品热暴露7天。在约80℃温度下运行测试约1小时。测试结果在下文显示于表1中。
表1:
表1中的结果表明清除剂能够将硫化氢含量从12500ppm减少到0ppm,提供100%减少,其中高TDS和低TDS盐水均以流体介质表示。观测到高TDS盐水中针对纯样品的硫化氢最终蒸气含量不降低到0ppm。这会是由于在高TDS盐水中存在更高浓度的溶解的钠和氯离子,其影响清除剂的质量转移。相较于低TDS盐水,清除剂分子需要更多的时间以溶解于高TDS盐水中。如果运行同一测试的滞留时间更长,那么发明人可以获得0ppm的最终蒸气浓度。
最终产品的热暴露样品能够减少硫化氢含量,效率在约86%-99%范围内。相较于纯样品,热暴露样品的清除性能的略微降低可以归于加热后样品粘度的增加。随着流体粘度增加,由于清除剂分子的流动性更低,清除剂与H2S的分子相互作用降低。这导致质量转移缓慢下降,因此清除效率降低。
还结合本申请中所公开的某些清除剂进行腐蚀性评估。使用静态高压釜测试程序进行腐蚀评估,以在停滞条件下在高温和高压下评估全面和点状腐蚀。
设定静态高压釜测试以产生LPR数据并且电极也充当质量损失试片。所使用的试片为C-1018(软钢)和K-55。K-55试片是具有低含量的镍和硅的高性能合金。其经过沉淀硬化并且展现高强度、可接受的电导率以及良好的弯曲特性。此外,其在高达约200℃的高温下拥有极佳的抗应力松弛性。试片尺寸是1/4"直径?1"长度,在一端具有A5-40螺纹孔并且暴露的试片面积是5.30cm2。高压釜材料是具有350mL容量的赫史特合金(Hastelloy)C-276。在安裝电极并且组装所有部件后,将高压釜用CO2和真空脱气三次。随后使用真空将300mL的清除剂:
(纯的,不经过热暴露,含有溶解氧)转移到高压釜中。在馈入流体后,在所需CO2下将高压釜加热到约200℃。每10分钟对每一个通道采集LPR测量结果。程序持续约21天。使高压釜冷却并且减压后,移出电极,在受抑制HCl中清洁,干燥并且称量以获得全面腐蚀率。此外,用显微镜评估电极的局部化攻击。来自这一测试的数据指示对于“k”=1的组合物,腐蚀率在约0.04与约0.1mmpy之间。
当前公开的清除剂也是热稳定的。如图1中可看出,所述图1涉及“k”=1的化合物,对清除剂:
进行热解重量分析并且结果指示清除剂在200℃下是热稳定的。
热解重量分析是一种热分析方法,其中根据增加的温度或根据时间来测量物质的物理和化学特性的变化。其是用以通过监测在加热样本时所发生的重量变化来确定物质的热稳定性并且测定其挥发性组分的分数的分析技术。通常在空气中或在惰性气氛(如氦气或氩气)中进行测量,并且根据增加的温度记录重量。
一般来说,将样品添加到通过精密天平支撑的样品盘中。盘驻留在炉中并且可以在实验期间加热或冷却。在实验期间监测样品的质量。样品净化气体控制样品环境。随后根据Y坐标上的重量百分比和X坐标上的温度或时间显示热曲线。
通过热解重量分析来分析活性H2S清除剂的热稳定性。在一些实施例中,活性H2S清除剂可能不具有100%活性并且在合成后可能含有痕量的非活性组分。如图1中所示的曲线显示在热解重量分析中在200℃下仍存在约86%的清除剂。这对应于如针对评估所制备的活性清除剂的初始产生浓度。
也对清除剂进行动态结垢循环(dynamic scale loop,DSL)测试:
以显示结垢抑制剂不需要与本申请的清除剂一起使用。当前公开的清除剂在其显示压差降低之前消耗较长时间段。
本文所公开和要求的所有组合物和方法都可以根据本公开在无不当实验的情况下制备和执行。虽然本发明可以按许多不同形式实施,但本文中详细描述了本发明的特定优选实施例。本公开是本发明的原理的范例并且不打算使本发明限于所说明的特定实施例。另外,除非明确相反地陈述,否则术语“一”的使用打算包括“至少一个/至少一种”或“一个或多个/一种或多种”。举例来说,“清除剂”打算包括“至少一种清除剂”或“一种或多种清除剂”。
按绝对术语或按近似术语给出的任何范围打算涵盖两者,并且本文所使用的任何定义打算为澄清的并且不为限制性的。尽管阐述本发明的广泛范围的数值范围和参数是近似值,但具体实例中所阐述的数值是尽可能精确报道的。但是,任何数值固有地含有某些由其对应测试测量值中所发现的标准差必然造成的误差。此外,本文所公开的所有范围应理解为涵盖其中包含的任何和所有子范围(包括所有分数值和整体值)。
此外,本发明涵盖本文所描述的各种实施例中的一些或全部的任何和所有可能组合。还应理解,对本文所描述的本发明优选实施例的各种改变和修改将为所属领域的技术人员显而易知。这类变化和修改可以在不脱离本发明的精神和范围的情况下并且在不减小其预期优势的情况下作出。因此,预期这类变化和修改由所附权利要求书涵盖。
Claims (20)
1.一种处理流中的硫化氢的方法,包括:
向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中所述C1-C6环结构可以是芳香族或环状脂肪族的;
C1-C6可以独立地选自碳、氮、氧以及硫,其中C2可以存在或不存在,并且如果不存在,那么所述环结构是五元环结构;
其中C2-C4可以独立地选自基团:X-R-{(OCH2)kOH}m;
其中所述环结构可以被拉电子基团或供电子基团取代;
X可以选自由以下组成的组:碳、氮、氧、硫、羰基、烷基以及烯基;
R可以选自由以下组成的组:氢、烷基、烯基、炔基、氮以及氧,其中所述烷基、烯基以及所述炔基可以未被取代或被取代;
k是选自0到25的整数;并且
m是选自1到4的整数。
2.根据权利要求1所述的方法,其中所述环结构是芳香族的,X是N(NH),R是C1-C8烷基,并且k+m=18。
3.根据权利要求1所述的方法,其中所述环结构是芳香族的,X是NCH2OH,R是C1-C8烷基,并且k+m=7。
4.根据权利要求1所述的方法,其中所述清除剂化合物包含式:
其中M1-M3独立地选自由以下组成的组:直链或分支链烷基、直链或分支链烯基、直链或分支链炔基、CHO、CN、COOH、C(O)R1、NO2、Cl、I、胺、被取代的胺、醇、醚、苯基、烯基酰胺基以及其任何组合,其中R1是烷基。
5.根据权利要求1到4中任一项所述的方法,其中所述流是液体流或气态流。
6.根据权利要求1到4中任一项所述的方法,其中所述流包含一种或多种烃。
7.根据权利要求1到6中任一项所述的方法,其中所述组合物排除三嗪化合物。
8.根据权利要求1到7中任一项所述的方法,其中所述组合物包含选自由以下组成的组的溶剂:异丙醇、甲醇、甲苯、水、二甲苯、乙二醇、丙二醇以及其任何组合。
9.根据权利要求8所述的方法,其中所述溶剂包含约10重量%到约99重量%的所述一种或多种清除剂化合物。
10.根据权利要求8所述的方法,其中所述溶剂包含约30重量%到约70重量%的所述一种或多种清除剂化合物。
11.根据权利要求1到10中任一项所述的方法,其中所述一种或多种清除剂在约200℃的温度下是热稳定的。
12.根据权利要求1到11中任一项所述的方法,其中所述组合物包含一种或多种选自由以下组成的组的添加剂:沥青烯抑制剂、石蜡抑制剂、腐蚀抑制剂、结垢抑制剂、乳化剂、水澄清剂、分散剂、破乳剂、额外硫化氢清除剂、气体水合物抑制剂、杀生物剂、pH调节剂、表面活性剂、溶剂以及其任何组合。
13.根据权利要求1到12中任一项所述的方法,其中所述流用于原油或天然气的生产、运输、储存和/或分离中。
14.根据权利要求1到13中任一项所述的方法,其中所述流在燃煤工艺、废水工艺、农场、屠宰厂、土地填筑、采矿操作、纸浆和纸设施或生物燃料工艺中使用或制造。
15.根据权利要求1到14中任一项所述的方法,其中所述方法使所述流中的所述硫化氢量降低约85%到约100%。
16.根据权利要求1到15中任一项所述的方法,其中添加到所述流中的所述一种或多种清除剂化合物的量与所述硫化氢的量的比率是约1:1到约30:1。
17.根据权利要求1到16中任一项所述的方法,其中所述一种或多种清除剂化合物无腐蚀性。
18.根据权利要求1到17中任一项所述的方法,其中所述一种或多种清除剂化合物经过热暴露。
19.一种处理流中的硫化氢的方法,包括:
向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中所述C1-C6环结构可以是芳香族或环状脂肪族的;
C1-C6可以独立地选自碳、氮、氧以及硫,其中C2可以存在或不存在,并且如果不存在,那么所述环结构是五元环结构;
其中所述环结构可以被拉电子基团或供电子基团取代;
X可以选自由以下组成的组:N(NH)、(NCH2OH)以及O;
R可以选自由以下组成的组:C2-C8直链或分支链烷基、C2-C8直链或分支链烯基以及C2-C8直链或分支链炔基;
Y是氮或氧;
k是选自0到25的整数;并且
m是选自1到4的整数。
20.一种处理流中的硫化氢的方法,包括:
向包含一定量的硫化氢的流中添加组合物,其中所述组合物包含具有以下通式的一种或多种清除剂化合物:
其中每一个C1-C6环结构可以是芳香族或环状脂肪族的;
C1-C6可以独立地选自碳、氮、氧以及硫,其中每一个C6可以存在或不存在,并且如果不存在,那么所述环结构是五元环结构;
其中所述环结构可以被拉电子基团或供电子基团取代;
每一个X独立地选自由以下组成的组:N、NH以及O;
每一个R独立地选自由以下组成的组:O、C1-C8直链或分支链烷基、C1-C8直链或分支链烯基以及C1-C8直链或分支链炔基;
每一个k是选自0到25的整数;并且
每一个m是选自1到4的整数。
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BR112017021486A2 (pt) | 2018-07-10 |
SA517390146B1 (ar) | 2022-05-12 |
US11085002B2 (en) | 2021-08-10 |
AU2016250539B2 (en) | 2020-06-11 |
AR104373A1 (es) | 2017-07-19 |
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WO2016172275A1 (en) | 2016-10-27 |
EP3286175B1 (en) | 2020-12-02 |
CA2982407A1 (en) | 2016-10-27 |
US20160312141A1 (en) | 2016-10-27 |
AU2016250539A1 (en) | 2017-10-12 |
CO2017009542A2 (es) | 2017-12-15 |
DK3286175T3 (da) | 2021-01-04 |
CA2982407C (en) | 2022-03-15 |
EP3286175A1 (en) | 2018-02-28 |
CN107438601B (zh) | 2020-11-13 |
US10308886B2 (en) | 2019-06-04 |
BR112017021486B1 (pt) | 2022-03-22 |
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