CN1274883C - corrosion inhibitor composition and its preparation and use - Google Patents
corrosion inhibitor composition and its preparation and use Download PDFInfo
- Publication number
- CN1274883C CN1274883C CN 03128264 CN03128264A CN1274883C CN 1274883 C CN1274883 C CN 1274883C CN 03128264 CN03128264 CN 03128264 CN 03128264 A CN03128264 A CN 03128264A CN 1274883 C CN1274883 C CN 1274883C
- Authority
- CN
- China
- Prior art keywords
- amine
- polyoxyethylene ether
- corrosion inhibitor
- ether phosphate
- alcohol polyoxyethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000005260 corrosion Methods 0.000 title claims abstract description 79
- 230000007797 corrosion Effects 0.000 title claims abstract description 77
- 239000003112 inhibitor Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002253 acid Substances 0.000 claims abstract description 37
- 150000001412 amines Chemical class 0.000 claims abstract description 32
- 239000008367 deionised water Substances 0.000 claims abstract description 25
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 25
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012964 benzotriazole Substances 0.000 claims abstract description 24
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 48
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 48
- 229910019142 PO4 Inorganic materials 0.000 claims description 31
- 239000010452 phosphate Substances 0.000 claims description 31
- -1 Cycloalkyl amine Chemical class 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 30
- 239000002131 composite material Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 23
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 235000010755 mineral Nutrition 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 14
- 229960001124 trientine Drugs 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- IWLXWEWGQZEKGZ-UHFFFAOYSA-N azane;zinc Chemical compound N.[Zn] IWLXWEWGQZEKGZ-UHFFFAOYSA-N 0.000 claims description 9
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 238000004523 catalytic cracking Methods 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000007670 refining Methods 0.000 claims description 7
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- HFXKQSZZZPGLKQ-UHFFFAOYSA-N cyclopentamine Chemical compound CNC(C)CC1CCCC1 HFXKQSZZZPGLKQ-UHFFFAOYSA-N 0.000 claims description 3
- 229960003263 cyclopentamine Drugs 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003141 primary amines Chemical group 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 12
- 239000011701 zinc Substances 0.000 abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract 1
- 150000007522 mineralic acids Chemical class 0.000 abstract 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- 239000003921 oil Substances 0.000 description 19
- 235000011187 glycerol Nutrition 0.000 description 17
- 230000005764 inhibitory process Effects 0.000 description 16
- 231100001010 corrosive Toxicity 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000013019 agitation Methods 0.000 description 7
- 239000010779 crude oil Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 241000282326 Felis catus Species 0.000 description 6
- 230000000116 mitigating effect Effects 0.000 description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 description 6
- 208000016261 weight loss Diseases 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- ZXVOCOLRQJZVBW-UHFFFAOYSA-N azane;ethanol Chemical compound N.CCO ZXVOCOLRQJZVBW-UHFFFAOYSA-N 0.000 description 5
- 230000006837 decompression Effects 0.000 description 5
- 230000003628 erosive effect Effects 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002461 imidazolidines Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000010962 carbon steel Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical group C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 150000002462 imidazolines Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 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
- 239000010865 sewage Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GDLILLGJYJOJLZ-UHFFFAOYSA-N C(CCC)O.N1N=NC2=C1C=CC=C2 Chemical compound C(CCC)O.N1N=NC2=C1C=CC=C2 GDLILLGJYJOJLZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical group C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
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- 238000004140 cleaning Methods 0.000 description 1
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- 230000023556 desulfurization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention discloses a corrosion inhibitor composition and a preparation and application method thereof. The composition is composed of 20 to 45 wt% of divalent alcohol polyethenoxy ether ammonium phosphate salt or trivalent alcohol polyethenoxy ether ammonium phosphate salt, 0 to 10 wt% of benzotriazole, 2 to 10 wt% of zinc and ammonia/amine complex of inorganic acids, 0 to 20 wt% of an organic solvent and deionized water as the rest. The inhibitor composition of the present invention is applicable to various acid corrosive environments where H2S exists, and the preparation thereof has the characteristics of available raw materials and simple and convenient production.
Description
Technical field
The present invention relates to metallic corrosion and suppress the field, particularly relate to a kind of novel corrosion inhibitor composition and method of making the same and application that is used for the acid attack environment.
Background technology
In recent years, domestic refinery is along with the increase of Middle East sulphur-bearing crude amount of finish, and domestic crude oil constantly the acid number and the sulphur content that are caused of exploitation increase year by year, etching problem shows more and more outstandingly on oil refining apparatus, H
2S or S form complicated and diversified corrosion system with other corrosive mediums in different device.That exist in the crude oil and progressively decompose generation H
2S, NaCl, CaCl
2, MgCl
2The HCl that produces Deng the inorganic salt hydrolysis, and water of condensation (comprising the water, the anticorrosion water filling of cat head three notes technologies that originally contain in the water that produces owing to pyrolysis in the still-process, the crude oil) have constituted the condensation of ordinary decompression column top, cooling system HCl-H
2S-H
2O type corrosion system.Nitride in the crude oil decomposes the HCN that produces, with H
2S and H
2O has constituted the HCN-H of catalytic cracking unit fractionation cat head
2S-H
2O type corrosion system.Stablize positions such as position, dry gas in the product purification device and desulfuration of liquefied gas in the catalytic cracking unit absorption, by H
2S and H
2The wet hydrogen sulfide corrosion environment that O constitutes, i.e. H
2S-H
2The O corrosion system.In the exploitation of oil-gas field process, can produce big water gaging, and extraction oil gas is often with a large amount of H
2S, CO
2Deng corrosives, so that form H at oil gas well, oil pipe, sleeve pipe, crude oil gathering system
2S-CO
2-H
2The corrosion system of O; Oilfield sewage salinity height contains H
2S, CO
2, dissolved oxygen, the pipeline of disposing polluted water in oil and return water system and facility be ubiquity H also
2S-CO
2-H
2The corrosion phenomenon of O.The common feature of these corrosion systems is that corrosive medium all is the electrolyte solution that is made of mineral acid (strong acid or weak acid) and water.
The seriously corroded of equipment and pipeline has influenced the length of production operation, steady, peace, full, excellent running in oil refining process and exploitation of oil-gas field and the defeated process of collection, has increased facility investment and production cost, has reduced the economic benefit of refinery and oil-gas field.For the inhibition of equipment corrosion generally from selecting many-sides such as corrosion-resistant material, technology are anticorrosion, filling inhibiter start with simultaneously, corrosion as ordinary decompression column top condensation cooling system, the refinery generally adopts the anticorrosion means of technology of " takes off three notes " both at home and abroad, promptly annotate ammonia, water filling, notes inhibiter, though annotate ammoniacal liquor can in and acid HCl, H in the corrosion system
2S, but also be simultaneously that NH takes place equipment
4The major cause of Cl underdeposit corrosion; and because ammoniacal liquor has different solubleness with acid in the process of temperature variation; during ammoniacal liquor can not be dissolved in the lime set rapidly when dew-point temperature and acid; annotate organic amine cost costliness, so current many investigators just are being devoted to study the acid that not only can neutralize in the acid corrosive medium but also can forming the inhibiter of compact protective film (as chemical films, adsorption film etc.) in the metallic surface.General commonly used oil field system inhibiter such as propiolic alcohol, pyridines, imidazolines have certain corrosion mitigating effect under lesser temps and solutions of weak acidity, but generally can not suppress the corrosion of iron and steel under 2～5 strong acidic condition and the hot conditions more than 90 ℃ effectively at distillation cat head pH value.
The mechanism of corrosion of metal in the acid attack environment is consistent with general galvanic corrosion essence, in the electrolyte solution environment, many impurity owing to distributing on the metallic surface, when it contacts with electrolyte solution, each impurity all can become negative electrode or anode for metal itself, so just must have many small negative electrodes or anode in whole metallic surface exists simultaneously, thereby form a lot of small galvanic cells, lose electronics at anode place metal and become metal ion and enter in the solution, the material that can be absorbed electronics at negative electrode place electronics is accepted.
Inhibiter to the corrosion inhibition of metal mainly be by physical adsorption and chemisorption in the metallic surface film forming, promptly the polar group in the inhibiter molecule is adsorbed on the metallic surface and has changed double electrical layers, has improved the activation energy of metal ion process.And the non-polar group in the inhibiter becomes to align away from metal, forms the hydrophobic protective membrane of one deck, becomes corrosive medium erosive barrier, thereby corrosion is inhibited.
Facts have proved that the application of inhibiter can suppress and alleviate the corrosion of equipment effectively, Research on Corrosion Inhibitor starts from the '30s in last century, still has many companies to be devoted to the exploitation in this field so far in the world.At present, the inhibiter that refinery's atmospheric and vacuum distillation unit, oil field system are used more is an imidazolidine derivatives, as patent US5300235, US5174957, CN1091781A is disclosed is a class oil soluble imidazoline amide compound, the imidazolinium compounds ring texture is decomposed to form mud easily, makes oil, emulsifying water easily after further carboxylic acid changes into salt.US6303079 discloses that by the quaternary amine salinization oil soluble imidazolinium compounds to be converted into water-soluble, this class inhibiter has certain corrosion mitigating effect at tower top condensing system, but can not be well carry out compositely, influenced its application at ordinary decompression column top condenser system strong acid corrosive environment with organic amine.US5368774 is open to be that the inhibiter of main ingredient is used for suppressing CO in the oil refining process with alkyl pyridine and sulfocompound (as thiocarbamide)
2Corrosion.It is the inhibiter of main ingredient that US5902515, US5961885 disclose with tetrahydroglyoxaline, alkyl pyridine, dispersion agent, is used for suppressing to contain hydrocarbon, the water mixture of sour gas.US5556575 discloses hydrocarbyl succinic acid anhydrides amine inhibiter, and the reaction product of alpha-olefin succinyl oxide and polyethylene polyamine is at HCl-H
2S-H
2Corrosion inhibition rate reached 95% when filling rate was 20ppm in the O system.US6013200 discloses the reaction product inhibiter with thiocarbamide and diethylenetriamine, is constantly feeding CO
266 ℃ of brinish etching systems in corrosion inhibition rate can reach more than 99%.
Make a general survey of existing inhibiter prior art, the problem that the inhibiter of being touched upon exists mainly is:
(1) most of inhibiter adaptability are not strong, are only applicable to a kind of corrosion system.More general imidazolines inhibiter character is stable inadequately, decomposes easily under alkaline condition, can not be effectively composite with organic amine, influenced its use under the strongly-acid corrosive environment.
(2) inhibition efficiency of inhibiter is not high.
Summary of the invention
The present invention be directed to the not strong and/or not high shortcoming of inhibition efficiency of inhibiter suitability in the prior art, the novel corrosion inhibitor that a kind of suitability is strong and inhibition efficiency is high composition is provided.The present invention also provides the preparation method and the application of this composite corrosion inhibitor in addition.
Composite corrosion inhibitor provided by the invention is made up of following component:
The dibasic alcohol polyoxyethylene ether phosphate ammonium salt of 20～45 weight % or trivalent alcohol polyoxyethylene ether phosphate ammonium salt;
The benzotriazole of 0～10 weight %;
2～10 weight % mineral acid zinc ammonia/amine complexes;
0～20 weight % organic solvent;
With the surplus deionized water.
Benzotriazole is an optional ingredient, and best compositing range is 5～10 weight %, and organic solvent recommendation this moment compositing range is 2.5～20 weight %, and best compositing range is 5～20 weight %.
Wherein dibasic alcohol polyoxyethylene ether phosphate ammonium salt is the reaction product of dibasic alcohol polyoxyethylene ether phosphate and ammoniacal liquor or organic amine, and its general structure as the formula (1); Trivalent alcohol polyoxyethylene ether phosphate ammonium salt is the reaction product of trivalent alcohol polyoxyethylene ether phosphate and ammoniacal liquor or organic amine, and its general structure as the formula (2).
M, n or k are 3～5 integers in the formula; A is ammonium ion or organic ammonium ion; X in the formula (1) is 0～2 integer; R1 and R2 are H, methyl or ethyl; Y, z in the formula (2) is 0～1 integer; R3 and R4 are H or methyl.
The general structure of benzotriazole as the formula (3),
Mineral acid zinc ammonia/amine complex is the product that is formed by ammoniacal liquor or organic amine and the complexing of mineral acid zinc salt, and the mineral acid zinc salt recommends to use zinc sulfate, zinc acetate or zinc carbonate etc., preferably zinc sulfate.
Organic solvent is C
1～C
9Alcohols, recommend to use methyl alcohol, ethanol, propyl alcohol, butanols or octanol etc.
Above dibasic alcohol in the described dibasic alcohol polyoxyethylene ether phosphate recommend to make spent glycol, 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol or 1,4 butyleneglycol etc., preferably ethylene glycol; Trivalent alcohol in the described trivalent alcohol polyoxyethylene ether phosphate recommends to use glycerol or 1,2,4-trihydroxybutane etc., preferably glycerol.Described organic amine can be primary amine or secondary amine, as C
2～C
6Alkylamine or Cycloalkyl amine, C
2～C
4Hydramine or various polyethylene polyamines etc.C
2～C
6Alkylamine recommend to use Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, quadrol or butanediamine etc.; Cycloalkyl amine recommends to use ring butylamine, cyclopentamine or hexahydroaniline etc.; C
2～C
4Hydramine recommend to use Monoethanolamine MEA BASF or diethanolamine etc., polyethylene polyamine recommends to use diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc.Organic amine preferably uses quadrol, hexahydroaniline, Monoethanolamine MEA BASF, diethylenetriamine or triethylene tetramine.
The present invention also provides the preparation method of composite corrosion inhibitor, it is characterized in that this method comprises the steps:
The first step: under normal temperature and pressure conditions, in dibasic alcohol polyoxyethylene ether phosphate or trivalent alcohol polyoxyethylene ether phosphate, add deionized water, add ammoniacal liquor or organic amine again and carry out neutralization reaction, reaction times is 20 minutes～1 hour, the trivalent alcohol polyoxyethylene ether phosphate ammonium salt of the dibasic alcohol polyoxyethylene ether phosphate ammonium salt of generating structure formula (1) or structural formula (2).Described dibasic alcohol is recommended to make spent glycol, 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol or 1,4 butyleneglycol etc., preferably ethylene glycol; Trivalent alcohol recommends to use glycerol or 1,2,4-trihydroxybutane etc., preferably glycerol.Described organic amine can be primary amine or secondary amine, as C
2～C
6Alkylamine or Cycloalkyl amine, C
2～C
4Hydramine or various polyethylene polyamines etc.C
2～C
6Alkylamine recommend to use Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, quadrol or butanediamine etc.; Cycloalkyl amine recommends to use ring butylamine, cyclopentamine or hexahydroaniline etc.; C
2～C
4Hydramine recommend to use Monoethanolamine MEA BASF or diethanolamine etc., polyethylene polyamine recommends to use diethylenetriamine, triethylene tetramine, tetraethylene pentamine etc.Organic amine preferably uses quadrol, hexahydroaniline, Monoethanolamine MEA BASF, diethylenetriamine or triethylene tetramine.The weight percent of each raw material is in this reaction:
Dibasic alcohol polyoxyethylene ether phosphate or trivalent alcohol polyoxyethylene ether phosphate 20～65%
Ammoniacal liquor or organic amine 5～20%
The deionized water surplus;
Second step: structural formula benzotriazole as the formula (3) is dissolved in the organic solvent at normal temperatures and pressures, and the part by weight of benzotriazole and organic solvent is 1: 05～1: 2, and preferably 1: 1～1: 2, wherein organic solvent was C
1～C
9Alcohols, particularly methyl alcohol, ethanol, propyl alcohol, butanols or octanol etc.;
The 3rd step: the mineral acid zinc salt is dissolved in the deionized water, and the part by weight scope of mineral acid zinc salt and deionized water is 1: 1～1: 5, adds ammoniacal liquor or organic amine then to generating stable complex solution;
The 4th step: benzotriazole solution, the mineral acid zinc ammonia in the 3rd step/amine complex solution of the preparation of second step are added in the first step reaction product, and mixing and stirring promptly gets inhibiter of the present invention.
Composite corrosion inhibitor of the present invention can be used for the refining of petroleum and the petrochemical complex course of processing, be specially adapted on the equipment of complete processing devices such as atmospheric and vacuum distillation, catalytic cracking, reformation, hydrotreatment, hydrofining, the process device that is particularly useful for gas stripping column, hydrogenation unit and hydrodesulfurization unit water cooler, high-pressure separator and the downstream thereof of atmospheric and vacuum distillation cat head condenser system, catalytic cracking fractionating tower top and absorbing-stabilizing system, dry gas and LPG Desulfurization part, sour water air-lift device, the prefractionation cat head of reformer.The present invention also can be used for the correlated process and the equipment of oil-gas field generation acid corrosion, especially the pipeline and the facility of oil gas well, oil pipe, sleeve pipe, crude oil gathering system and disposing polluted water in oil and return water system.Its application method is: composite corrosion inhibitor is added in the working fluid of the above-mentioned course of processing, add-on is 5～80 μ g/g, is recommended as 10～50 μ g/g, is preferably 10～30 μ g/g.
Above-mentioned working fluid is meant that all comprise H
2The oil refining of acid corrosion and logistics, oil-gas field production, the oilfield sewage that chemical industry equipment is processed particularly take place in the logistics of the various acid attack media of S.
Composite corrosion inhibitor provided by the present invention, owing to introduced a plurality of polyoxyethylene groups in its component dibasic alcohol polyoxyethylene ether phosphate that contains or the trivalent alcohol polyoxyethylene ether phosphate, therefore on the metallic surface, has stronger adsorptive power than general phosphoric acid ester, thereby strengthened corrosion inhibition, but also eliminated the shortcoming of general phosphoric acid ester phosphorus oxygen key facile hydrolysis, this component through with ammoniacal liquor or organic amine salify after, further strengthened its corrosion inhibition, stable in properties not only, facile hydrolysis not, and can be with organic amine with arbitrarily than composite, composite product is in stable condition, can be used for the strongly-acid corrosive environment of ordinary decompression column top condenser system.The component benzotriazole that contains in the said composition in addition has synergy with polyvalent alcohol polyoxyethylene ether phosphate amine salt, and composite together the use can strengthen corrosion mitigating effect.The composite use of component mineral acid zinc salt and phosphoric acid ester and benzotriazole has synergistic function.So composite corrosion inhibitor of the present invention compared with prior art: 1) suitability is wide, applicable to all H
2The various acid attack environment that S exists can be used for oil refining apparatus, as the condensation of ordinary decompression column top, cooling system HCl-H
2S-H
2The HCN-H of O type strongly-acid corrosive environment, catalytic cracking unit fractionation cat head
2S-H
2O type acid attack environment; Catalytic cracking unit absorbs the wet hydrogen sulfide corrosion environment at positions such as the dry gas stablize in position, the product purification device and desulfuration of liquefied gas, i.e. H
2S-H
2The O corrosive environment; Can be used for again oil extraction process gas also, the CO at position such as oil well, oil pipe, sleeve pipe and crude oil gathering system
2-H
2S-H
2O acid attack environment; 2) this inhibiter can with organic amine carry out composite, stable performance, inhibition efficiency height; 3) preparation of this inhibiter has starting material and is easy to get, and produces simple and easy to do characteristics.
Embodiment
Describe the present invention in detail with specific embodiment below, but embodiment does not limit the scope of the invention.
Embodiment 1
The first step: preparation structural formula compound (numbering A) as the formula (4)
At normal temperatures and pressures, in the there-necked flask that magnetic agitation, thermometer, prolong, dropping funnel are housed, add the 40g deionized water, 82g ethylene glycol polyoxyethylene ether phosphate, under constantly stirring, slowly drip 13g ammoniacal liquor, dropwised in 30 minutes, to obtain concentration in 30 minutes be 70.3% ethylene glycol polyoxyethylene ether phosphate ammonium salt solution in reaction under constantly stirring, and the cooling back is standby.
Second step: take by weighing the 20g benzotriazole and be dissolved in the 20g ethanol, stir until dissolving fully, stand-by.
The 3rd step: 10g zinc sulfate is dissolved in the 15g deionized water, slowly drip 10g ammoniacal liquor again to generating stable zinc ammonia complex, stand-by.
The 4th step: the compd A of the second step benzotriazole ethanolic soln, the 3rd step zinc ammonia complex and the first step gained is mixed, obtain active principle content and be 64.2% inhibiter sample, be designated as CI-01.
Embodiment 2
The first step: preparation structural formula compound (numbering B) as shown in Equation 5
At normal temperatures and pressures, in the there-necked flask that magnetic agitation, thermometer, prolong, dropping funnel are housed, add the 65g deionized water, 82g glycerol polyoxyethylene ether phosphate, under constantly stirring, slowly drip the 18g monoethanolamine, dropwised in 30 minutes, to obtain concentration in 30 minutes be 60.6% glycerol polyoxyethylene ether phosphate single ethanol ammonium salt solution in reaction under constantly stirring, and the cooling back is standby.
Second step: take by weighing the 20g benzotriazole and be dissolved in the 35g butanols, stir until dissolving fully, stand-by.
The 3rd step: 10g zinc sulfate is dissolved in the 15g deionized water, and slow again Dropwise 5 g monoethanolamine is to generating stable zinc amine complex, and is stand-by.
The 4th step: the compd B of the second step benzotriazole butanol solution, the 3rd step zinc ammonia complex and the first step gained is mixed, obtain active principle content and be 54% inhibiter sample, be designated as CI-02.
Embodiment 3
The first step: preparation structural formula compound (numbering C) as shown in Equation 6
At normal temperatures and pressures, in the there-necked flask that magnetic agitation, thermometer, prolong, dropping funnel are housed, add the 23g deionized water, 70g glycerol polyoxyethylene ether phosphate, under constantly stirring, slowly drip the 25g triethylene tetramine, dropwised in 30 minutes, to obtain concentration in 30 minutes be 80.5% glycerol polyoxyethylene ether phosphate single ethanol ammonium salt solution in reaction under constantly stirring, and the cooling back is standby.
Second step: take by weighing the 20g benzotriazole and be dissolved in the 40g ethanol, stir until dissolving fully, stand-by.
The 3rd step: 10g zinc sulfate is dissolved in the 50g deionized water, slowly drip the 10g triethylene tetramine again to generating stable zinc amine complex, stand-by.
The 4th step: the Compound C of the second step benzotriazole ethanolic soln, the 3rd step zinc amine complex and the first step gained is mixed, obtain active principle content and be 54.4% inhibiter sample, be designated as CI-03.
Embodiment 4
The first step: preparation structural formula compound (numbering D) as the formula (7)
At normal temperatures and pressures, in the there-necked flask that magnetic agitation, thermometer, prolong, dropping funnel are housed, add the 113g deionized water, 31g ethylene glycol polyoxyethylene ether phosphate, under constantly stirring, slowly drip the 9g monoethanolamine, dropwised in 30 minutes, to obtain concentration in 30 minutes be 26.1% ethylene glycol polyoxyethylene ether phosphate ammonium salt solution in reaction under constantly stirring, and the cooling back is standby.
Second step: take by weighing the 10g benzotriazole and be dissolved in the 20g ethanol, stir until dissolving fully, stand-by.
The 3rd step: 2.6g zinc sulfate is dissolved in the 13g deionized water, slowly drip the 1.4g monoethanolamine again to generating stable zinc amine complex, stand-by.
The 4th step: the Compound D of the second step benzotriazole ethanolic soln, the 3rd step zinc amine complex and the first step gained is mixed, obtain active principle content and be 27% inhibiter sample, be designated as CI-04.
Embodiment 5
The first step: the compound (numbering C) of preparation shown in structural formula (6) among the embodiment 3
At normal temperatures and pressures, in the there-necked flask that magnetic agitation, thermometer, prolong, dropping funnel are housed, add the 30g deionized water, 22g glycerol polyoxyethylene ether phosphate, under constantly stirring, slowly drip the 8g triethylene tetramine, dropwised in 20 minutes, to obtain concentration in 20 minutes be 50% glycerol polyoxyethylene ether phosphate single ethanol ammonium salt solution in reaction under constantly stirring, and the cooling back is standby.
Second step: take by weighing the 10g benzotriazole and be dissolved in the 15g ethanol, stir until dissolving fully, stand-by.
The 3rd step: 2.5g zinc sulfate is dissolved in the 10g deionized water, slowly drip the 2.5g triethylene tetramine again to generating stable zinc amine complex, stand-by.
The 4th step: the Compound C of the second step benzotriazole ethanolic soln, the 3rd step zinc amine complex and the first step gained is mixed, obtain active principle content and be 45% inhibiter sample, be designated as CI-05.
Embodiment 6
The first step: the compound (numbering C) of preparation shown in structural formula (6) among the embodiment 3
At normal temperatures and pressures, in the there-necked flask that magnetic agitation, thermometer, prolong, dropping funnel are housed, add the 30g deionized water, 22g glycerol polyoxyethylene ether phosphate, under constantly stirring, slowly drip the 8g triethylene tetramine, dropwised in 20 minutes, to obtain concentration in 20 minutes be 50% glycerol polyoxyethylene ether phosphate single ethanol ammonium salt solution in reaction under constantly stirring, and the cooling back is standby.
Second step: 2.5g zinc sulfate is dissolved in the 10g deionized water, slowly drip the 2.5g triethylene tetramine again to generating stable zinc amine complex, stand-by.
The 3rd step: the Compound C of second step zinc amine complex and the first step gained is mixed, obtain active principle content and be 46.7% inhibiter sample, be designated as CI-06.
Embodiment 7
The first step: the compound (numbering C) of preparation shown in structural formula (6) among the embodiment 3
At normal temperatures and pressures, in the there-necked flask that magnetic agitation, thermometer, prolong, dropping funnel are housed, add the 30g deionized water, 22g glycerol polyoxyethylene ether phosphate, under constantly stirring, slowly drip the 8g triethylene tetramine, dropwised in 20 minutes, to obtain concentration in 20 minutes be 50% glycerol polyoxyethylene ether phosphate single ethanol ammonium salt solution in reaction under constantly stirring, and the cooling back is standby.
Second step: the 5g zinc acetate is dissolved in the 10g deionized water, slowly drip the 4.5g triethylene tetramine again to generating stable zinc amine complex, stand-by.
The 3rd step: the Compound C of second step zinc amine complex and the first step gained is mixed, obtain active principle content and be 49.6% inhibiter sample, be designated as CI-07.
Embodiment 8
Evaluation (the HCl-H of inhibiter performance
2S-H
2The O corrosion system):
For investigating the performance of inhibiter, adopt the evaluation of classical static steel weight-loss method, concrete experimental procedure is as follows: put into the moisture eliminator cooling after No. 45 carbon steel test pieces are cleaned and dried with sherwood oil and acetone.Then the corrosive medium that configures is poured in the there-necked flask of a contact-carrying formula thermometer, prolong, the test piece after the accurate weighing being hung also is soaked in the corrosive medium fully again, be heated to corrosion temperature and kept 6 hours, take out test piece afterwards again through solvent cleaning, oven dry, cooling, weighing, calculate rate of weight loss, corrosion inhibition rate and erosion rate according to test piece changes in weight before and after the experiment.
G---the weight of test piece before the experiment, g G '---the weight of experiment back test piece, g
Δ G
Empty---the rate of weight loss of test piece during blank assay, % Δ G
Agent---the rate of weight loss of test piece when adding the inhibiter experiment, %
The surface-area of S---test piece, m
2T---the time that experiment is carried out, h
The density of ρ---test piece, kg/m
3
Configuration 505g concentration is 1000mg/L HCl-1000mg/L H
2The corrosive medium of S (theoretical value) is transferred to 6 with ammoniacal liquor with pH value, is used to estimate the corrosion inhibition rate of inhibiter, and the corrosion inhibition rate evaluation result of several inhibiter is as shown in table 1:
Table 1 HCl-H
2S-H
2The evaluation result of several inhibiter of O corrosion system
| The inhibiter sample | Corrosion inhibition rate % | Erosion rate mm/a |
| Imidazolidine derivatives | 55.86 | 2.24 |
| The glycerin polyoxyethylene ether phosphoric acid ester | 72.21 | 1.47 |
| Compd A | 79.36 | 1.05 |
| Compd B | 82.74 | 0.93 |
| Compound C | 86.78 | 0.77 |
| Compound D | 76.27 | 1.23 |
| Sample CI-01 | 91.36 | 0.69 |
| Sample CI-02 | 92.48 | 0.65 |
| Sample CI-03 | 94.85 | 0.57 |
| Sample CI-04 | 83.66 | 0.89 |
| Sample CI-05 | 88.47 | 0.70 |
| Sample CI-06 | 81.26 | 0.99 |
| Sample CI-07 | 78.66 | 1.11 |
*More than the filling rate of each sample in solution be 15 μ g/g.
As shown in Table 1, the corrosion mitigating effect of dibasic alcohol polyoxyethylene ether phosphate or trivalent alcohol polyoxyethylene ether phosphate is better than imidazolidine derivatives, form behind ammonia/amine salt that corrosion mitigating effect further strengthens and benzotriazole derivative, the composite back of zinc salt corrosion mitigating effect further improve.
Embodiment 9
Evaluation (the CO of inhibiter performance
2-H
2S-H
2The O corrosion system):
Configuration 505g concentration is 200mg/L CO
2-200mg/L H
2The S corrosive medium places the there-necked flask of being with stirring, thermometer, and No. 45 carbon steel test pieces are hung in the there-necked flask, and temperature is controlled at 25 ℃ and kept 6 hours.Accurately the weight of test piece before and after the weighing experiment is calculated weight loss and corrosion speed, and table 2 is at CO
2-H
2S-H
2In the O corrosion system to the evaluation result of several inhibiter.
Table 2 CO
2-H
2S-H
2The evaluation result of several inhibiter in the O corrosion system
| The inhibiter sample | Corrosion inhibition rate % | Erosion rate mm/a |
| Imidazolidine derivatives | 52.28 | 2.38 |
| The glycerin polyoxyethylene ether phosphoric acid ester | 70.02 | 1.56 |
| Compd A | 74.47 | 1.34 |
| Compd B | 77.23 | 1.17 |
| Compound C | 83.74 | 0.89 |
| Compound D | 72.13 | 1.46 |
| Sample CI-01 | 89.33 | 0.73 |
| Sample CI-02 | 90.21 | 0.71 |
| Sample CI-03 | 92.87 | 0.63 |
| Sample CI-04 | 75.76 | 1.28 |
| Sample CI-05 | 82.51 | 0.93 |
| Sample CI-06 | 72.27 | 1.44 |
| Sample CI-07 | 70.33 | 1.53 |
*More than the filling rate of each sample in solution be 15 μ g/g.
Embodiment 10
Evaluation (the H of inhibiter performance
2S-H
2The O corrosion system):
Configuration 505g concentration is 500mg/L H
2The S corrosive medium places the there-necked flask of being with stirring, thermometer, and No. 45 carbon steel test pieces are hung in the there-necked flask, and temperature is controlled at 45 ℃ and kept 6 hours.Accurately the weight of test piece before and after the weighing experiment is calculated weight loss and corrosion speed, and table 3 is at H
2S-H
2In the O corrosion system to the evaluation result of several inhibiter.
Table 3 H
2S-H
2The evaluation result of several inhibiter in the O corrosion system
| The inhibiter sample | Corrosion inhibition rate % | Erosion rate mm/a |
| Imidazolidine derivatives | 50.86 | 2.45 |
| The glycerin polyoxyethylene ether phosphoric acid ester | 75.17 | 1.29 |
| Compd A | 82.33 | 0.95 |
| Compd B | 85.51 | 0.82 |
| Compound C | 87.36 | 0.76 |
| Compound D | 77.18 | 1.19 |
| Sample CI-01 | 92.77 | 0.64 |
| Sample CI-02 | 94.41 | 0.58 |
| Sample CI-03 | 95.74 | 0.54 |
| Sample CI-04 | 80.73 | 1.02 |
| Sample CI-05 | 88.19 | 0.71 |
| Sample CI-06 | 79.26 | 1.09 |
| Sample CI-07 | 77.82 | 1.17 |
*More than the filling rate of each sample in solution be 15 μ g/g.
Claims (10)
1. composite corrosion inhibitor, it is characterized in that: said composition is made up of following component:
The dibasic alcohol polyoxyethylene ether phosphate ammonium salt of 20～45 weight % or trivalent alcohol polyoxyethylene ether phosphate ammonium salt;
The benzotriazole of 0～10 weight %;
Mineral acid zinc ammonia/amine complex of 2～10 weight %;
The organic solvent of 0～20 weight %;
With the surplus deionized water,
Wherein dibasic alcohol polyoxyethylene ether phosphate ammonium salt is the reaction product of dibasic alcohol polyoxyethylene ether phosphate and ammoniacal liquor or organic amine, and its general structure as the formula (1); Trivalent alcohol polyoxyethylene ether phosphate ammonium salt is the reaction product of trivalent alcohol polyoxyethylene ether phosphate and ammoniacal liquor or organic amine, its general structure as the formula (2),
M, n or k are 3～5 integers in the formula; A is ammonium ion or organic ammonium ion; X in the formula (1) is 0～2 integer; R1 and R2 are H, methyl or ethyl; Y, z in the formula (2) is 0～1 integer; R3 and R4 are H or methyl;
The general structure of benzotriazole as the formula (3),
Mineral acid zinc ammonia/amine complex is the complex compound of mineral acid zinc salt and ammoniacal liquor or organic amine;
Organic solvent is C
1～C
9Alcohols.
2. composite corrosion inhibitor according to claim 1 is characterized in that the content of benzotriazole in composition is 5～10 weight %, and the content of organic solvent in composition is 2.5～20 weight %.
3. composite corrosion inhibitor according to claim 1 is characterized in that: organic amine is primary amine or secondary amine; Organic solvent is methyl alcohol, ethanol, propyl alcohol, butanols or octanol; Described mineral acid zinc salt is zinc sulfate, zinc acetate or zinc carbonate.
4. composite corrosion inhibitor according to claim 3 is characterized in that: described organic amine is C
2～C
6Alkylamine or Cycloalkyl amine, C
2～C
4Hydramine or polyethylene polyamine.
5. composite corrosion inhibitor according to claim 4 is characterized in that: C
2～C
6Alkylamine be Tri N-Propyl Amine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, quadrol or butanediamine; Cycloalkyl amine is ring butylamine, cyclopentamine or a hexahydroaniline; C
2～C
4Hydramine be Monoethanolamine MEA BASF or diethanolamine; Polyethylene polyamine is diethylenetriamine, triethylene tetramine or tetraethylene pentamine.
6. according to claim 4 or 5 described composite corrosion inhibitors, it is characterized in that: organic amine is quadrol, hexahydroaniline, Monoethanolamine MEA BASF, diethylenetriamine or triethylene tetramine.
7. a method for preparing the described composite corrosion inhibitor of claim 1 is characterized in that this method comprises the steps:
The first step: under normal temperature and pressure conditions, in dibasic alcohol polyoxyethylene ether phosphate or trivalent alcohol polyoxyethylene ether phosphate, add deionized water, add ammoniacal liquor or organic amine again and carry out neutralization reaction, reaction times is 20 minutes～1 hour, the trivalent alcohol polyoxyethylene ether phosphate ammonium salt of the dibasic alcohol polyoxyethylene ether phosphate ammonium salt of generating structure formula (1) or structural formula (2), the weight percent of each raw material is in this reaction:
Dibasic alcohol polyoxyethylene ether phosphate or trivalent alcohol polyoxyethylene ether phosphate 20～65%
Ammoniacal liquor or organic amine 5～20%
The deionized water surplus;
Second step: structural formula benzotriazole as the formula (3) is dissolved in the organic solvent at normal temperatures and pressures, and the part by weight of benzotriazole and organic solvent is 1: 0.5～1: 2;
The 3rd step: the mineral acid zinc salt is dissolved in the deionized water, and the part by weight scope of mineral acid zinc salt and deionized water is 1: 1～1: 5, adds ammoniacal liquor or organic amine then to generating stable complex solution;
The 4th step: benzotriazole solution, the mineral acid zinc ammonia in the 3rd step/amine complex solution of the preparation of second step are added in the first step reaction product, and mixing and stirring promptly gets composite corrosion inhibitor.
8. the application of the described composite corrosion inhibitor of claim 1, it is characterized in that this composite corrosion inhibitor is used for the refining of petroleum and the petrochemical complex course of processing, method is that composite corrosion inhibitor is added in the working fluid of the above-mentioned course of processing, and add-on is 5～80 μ g/g.
9. the application of described composite corrosion inhibitor according to Claim 8 is characterized in that the described course of processing is atmospheric and vacuum distillation, catalytic cracking, reformation, hydrotreatment or hydrofining.
10. the application of described composite corrosion inhibitor according to Claim 8, the add-on that it is characterized in that composite corrosion inhibitor are 10～50 μ g/g.
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| CN101838811B (en) * | 2009-03-20 | 2012-10-03 | 杨江 | New special corrosion inhibitor for oil production |
| CN102828724B (en) * | 2011-06-17 | 2015-05-13 | 中国石油天然气股份有限公司 | Method for preventing hydrogen sulfide gas in repairing work of hydrogen sulfide contained oil well |
| CN103563894B (en) * | 2013-11-05 | 2015-07-01 | 石家庄博佳特化工有限公司 | Polyether phosphate pesticide tackifier and preparation method thereof |
| CN105018144A (en) * | 2015-06-23 | 2015-11-04 | 武汉三友石化有限公司 | Water-soluble corrosion inhibitor |
| US9828566B2 (en) * | 2015-07-06 | 2017-11-28 | Afton Checmical Corporation | Boron free corrosion inhibitors for metalworking fluids |
| CN106868515B (en) * | 2017-01-23 | 2019-03-19 | 麻城天安化工股份有限公司 | A kind of metal surface activation agent and preparation method thereof |
| CN107286370B (en) * | 2017-08-08 | 2019-06-25 | 青岛长荣化工科技有限公司 | A kind of nitrogen-phosphorus flame retardant and preparation method thereof |
| CN110129803B (en) * | 2019-04-12 | 2020-05-19 | 华中科技大学 | Copper corrosion inhibitor based on metal organic framework materials MOFs and preparation method thereof |
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