CN100560801C - Water-soluble high-temperature organic acid corrosion inhibitor and preparation method and use method thereof - Google Patents
Water-soluble high-temperature organic acid corrosion inhibitor and preparation method and use method thereof Download PDFInfo
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- CN100560801C CN100560801C CNB2006101125334A CN200610112533A CN100560801C CN 100560801 C CN100560801 C CN 100560801C CN B2006101125334 A CNB2006101125334 A CN B2006101125334A CN 200610112533 A CN200610112533 A CN 200610112533A CN 100560801 C CN100560801 C CN 100560801C
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- 150000007524 organic acids Chemical class 0.000 title claims abstract description 47
- 239000003112 inhibitor Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 7
- 238000005260 corrosion Methods 0.000 title abstract description 31
- 230000007797 corrosion Effects 0.000 title abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000005764 inhibitory process Effects 0.000 claims abstract description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001412 amines Chemical class 0.000 claims abstract description 11
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005696 Diammonium phosphate Substances 0.000 claims abstract description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 5
- KNQKRMVYLDOGCT-UHFFFAOYSA-N ammonium phosphate sulfate Chemical compound [NH4+].[NH4+].OP(O)([O-])=O.OS([O-])(=O)=O KNQKRMVYLDOGCT-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims abstract description 5
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012964 benzotriazole Substances 0.000 claims abstract description 5
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940073608 benzyl chloride Drugs 0.000 claims abstract description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims abstract description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims abstract description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 5
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims abstract description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 16
- -1 sulphur alkene Chemical class 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005864 Sulphur Substances 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229960004418 trolamine Drugs 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 abstract 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 229940087305 limonene Drugs 0.000 abstract 1
- 235000001510 limonene Nutrition 0.000 abstract 1
- 229960004063 propylene glycol Drugs 0.000 abstract 1
- 235000013772 propylene glycol Nutrition 0.000 abstract 1
- 239000001488 sodium phosphate Substances 0.000 abstract 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 abstract 1
- 235000019801 trisodium phosphate Nutrition 0.000 abstract 1
- 230000003628 erosive effect Effects 0.000 description 10
- 238000005292 vacuum distillation Methods 0.000 description 7
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a water-soluble high-temperature organic acid corrosion inhibitor, a preparation method and a use method thereof, wherein the preparation method comprises the following steps: 10-60% of corrosion inhibitor intermediate obtained by reacting boric acid and organic amine according to the molar ratio of 1: 0.5-3, and 20-80% of C1～C9Methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, 1, 2-propanediol, n-pentanol, n-heptanol, n-octanolThe corrosion inhibitor is a corrosion inhibition film forming component formed by combining monohydric alcohol or dihydric alcohol solvent formed by combining one or more than two of alcohols and one or more than two of 0.1-20% of thiourea, benzyl chloride, limonene, propiolic alcohol, trisodium phosphate, ammonium phosphate sulfate, diammonium phosphate, triammonium phosphate and benzotriazole, and is added into a naphthenic acid corrosion medium by 30-1000 mu g/g, so that the corrosion inhibitor is suitable for inhibiting the high-temperature naphthenic acid corrosion of a pressure reducing tower of a refinery at 200-400 ℃, and is resistant to the corrosion of hydrogen sulfide and hydrogen chloride, and the corrosion inhibition efficiency is over 90%.
Description
Technical field
The present invention relates to a kind of high-temperature organic acid inhibitor that is used to suppress 200～400 ℃ of refinery's vacuum distillation tower high-temperature naphthenic acid erosion environment.
Background technology
At present both at home and abroad about in the acid corrosion Research on Corrosion Inhibitor, mineral acid (example hydrochloric acid, mud acid etc.) Research on Corrosion Inhibitor is perfect relatively, the inhibiter of many superior performances such as CT1-3 etc. are arranged, do not appear in the newspapers and be used to suppress organic acid (as carboxylic acid, naphthenic acid etc.) corrosive Research on Corrosion Inhibitor.Organic acid corrosion is prevalent among the industrial production, and performance is the most outstanding is equipment corrosion in the oil refining course of processing.Because the current a large amount of processing import crude oil of China, wherein the part imported crude oil is high-sulfur, crude oil with high acid value, and in the course of processing, serious corrosion phenomenon can take place at enrichment organic acid position in the device.As when processing the Kelamayi naphthenic base crude, in the vacuum distillation tower more than 250 ℃ the naphthenic acid corrosion in zone very serious.At present, also there is certain defective in inhibiter in the refinery actual application: vacuum distillation tower high-temperature naphthenic acid erosion position etching problem is not basic for a long time to be solved, and causes that equipment and pipeline corrosion protection are serious; The inhibition efficiency of inhibiter is low, solubility property is relatively poor.Relevant with the present invention by retrieval patented technology has: CN 1388271A has introduced a kind of iron and steel inhibiter that is used for high-temperature acidic medium (below 160 ℃ for 20% hydrochloric acid or mud acid) and preparation method thereof; It is raw material synthetic imidazoline amide compound with organic amine and organic acid that CN 1091781A has introduced a kind of, is a kind of oil-soluble inhibitor, is used for the HCL-H of refinery atmospheric and vacuum distillation unit system
2S protection against corrosion technology process; CN 1422984A has introduced the inhibiter of a kind of imidazoline amide by the band aromatic nucleus, the imidazoline amide of being with straight chain and sulfur-bearing low molecular compound, alkynol, solvent composition, is a kind of HCL-H that is used for refinery atmospheric and vacuum distillation unit condensation cooling system (temperature is lower than 90 ℃)
2S corrosive corrosion inhibitor; It is raw material synthetic imidazoline type water soluble rust inhibitor with organic acid and polyamines polyene that CN 1546730A has introduced a kind of, is used for the HCN-H of refinery absorption-stabilization system by catalytic cracking (50 ± 1 ℃ of temperature)
2S-H
2The corrosion of O type; It is to add thiocarbamide and alkyl alcohol behind the raw material synthetic tetrahydroglyoxaline intermediate with lipid acid and part polyamines that CN 1277240A has introduced a kind of, makes oily molten aqueous dispersion type inhibiter, is applicable to that the oil field contains CO
2High salinity sewage (50～120 ℃ of temperature) to the erosion of metallic surface.Development is used to suppress particularly high temperature (more than 200 ℃) water-soluble organic acid inhibiter of organic acid corrosive, the at present domestic blank that still belongs to.
Summary of the invention
The object of the present invention is to provide a kind of can be applicable in the refining of petroleum and the petrochemical complex course of processing, suppress the corrosion of high-temperature organic acid, be specially adapted to suppress a kind of high-temperature organic acid inhibitor of 200～400 ℃ of refinery's vacuum distillation tower high-temperature naphthenic acid erosion environment pipeline and equipment.
Another object of the present invention is to provide the using method of above-mentioned inhibiter, the water-soluble high-temperature organic acid inhibitor that accounts for 30～1000 μ g/g of 200～400 ℃ of high-temperature organic acid corrosive mediums or the high-temperature naphthenic acid erosion medium-weight below 400 ℃ is added in the above-mentioned corrosive medium, and thorough mixing is even.
A further object of the invention is above-mentioned inhibiter can be applied in the petroleum refining process in 200～400 ℃ the high-temperature organic acid corrosive medium, particularly high-temperature naphthenic acid erosion medium.
The preparation method of one of technical scheme provided by the invention inhibiter is: the 1. preparation of high-temperature organic acid inhibitor intermediate: boric acid and organic amine were put in the there-necked flask in 1: 0.5 in molar ratio～1: 3, and add 5～30% the varsol account for boric acid and organic amine gross weight, under constantly stirring, be warming up to 100～300 ℃, refluxed 2～20 hours, when the reaction mixture acid number reached 3～20mgKOH/g, reaction finished, and obtains the high-temperature organic acid inhibitor intermediate; After the high-temperature organic acid inhibitor intermediate that 2. will account for water-soluble high-temperature organic acid inhibitor weight percent 10～60% is cooled to 60～70 ℃, add while stirring under normal pressure that to account for the water-soluble high-temperature organic acid inhibitor weight percent be 20～80% to be selected from C
1～C
9Methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, isopropylcarbinol, 1, monohydroxy-alcohol or diol solvent that in 2-propylene glycol, Pentyl alcohol, n-Heptyl alcohol, the n-Octanol one or both or two or more combination of components form, and to account for the water-soluble high-temperature organic acid inhibitor weight percent be 0.1～20% to be selected from a kind of in thiocarbamide, Benzyl Chloride, sulphur alkene, propiolic alcohol, tertiary sodium phosphate, ammonium phosphate sulfate, diammonium phosphate, triammonium phosphate, the benzotriazole or the inhibition film-forming components that combines of two or more component arbitrarily.With 1., 2. component is that 20～70 ℃, time are that the mode of 2～5h is concocted by the blending temperature, can make.
Wherein the organic amine in the high-temperature organic acid inhibitor intermediate is quadrol, N-hydroxyethyl-ethylenediamine, N-methyl, N-diethanolamine, methyl tertiary amine, Trimethylamine 99, diethanolamine, trolamine, N, N-two (lower alkyl) Propanolamine, N-methyl, N-ethylol amine, N-ethyl, N-ethylol amine, N-butyl, a kind of or any two kinds (containing two kinds) the above components in the N-ethylol amine combine.
Two of technical scheme provided by the invention is: add the described inhibiter of 30～1000 μ g/g to 200～400 ℃ high-temperature organic acid corrosive medium, particularly mix in the high-temperature naphthenic acid erosion medium.
Inhibiter of the present invention can effectively prevent the corrosion of unit and pipeline; Suitability of the present invention is wide, and not only the Applicable temperature scope is wide, and can suppress the corrosion of high-temperature organic acid to pipeline and equipment, is specially adapted to suppress 200～400 ℃ of refinery's vacuum distillation tower high-temperature naphthenic acid erosions.Simultaneously, this inhibiter has the good anti-H 2 S and the performance of hydrogen-chloride etching, therefore to other hydrogen sulfide and hydrogen-chloride etching system, and same being suitable for; And inhibiter of the present invention does not have influence to other oil refining injecting, stable performance, and inhibition efficiency is up to more than 90%; Produce simple and easy to doly, raw material is easy to obtain, and can effectively reduce cost.
Embodiment
Embodiment 1～18: the preparation of organic acid high-temperature corrosion inhibitor intermediate
Boric acid and organic amine were put in the there-necked flask in 1: 0.5 in molar ratio～1: 3, and add 5～30% the varsol account for acid compounds and organic amine gross weight, under constantly stirring, be warming up to 100～300 ℃, refluxed 2～20 hours, when the reaction mixture acid number reached 3～20mgKOH/g, reaction finished, and obtains the high-temperature organic acid inhibitor intermediate.
The embodiment of table 1 organic acid high-temperature corrosion inhibitor intermediate preparation
Embodiment 19～51: a kind of preparation of water-soluble high-temperature organic acid inhibitor
After the high-temperature organic acid inhibitor intermediate that accounts for water-soluble high-temperature organic acid inhibitor weight percent 10～60% is cooled to 60～70 ℃, add while stirring under normal pressure that to account for the water-soluble high-temperature organic acid inhibitor weight percent be 20～80% to be selected from C
1～C
9Methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, isopropylcarbinol, 1, the 2-propylene glycol, Pentyl alcohol, n-Heptyl alcohol, monohydroxy-alcohol or diol solvent that in the n-Octanol one or both or two or more combination of components form, and to account for the water-soluble high-temperature organic acid inhibitor weight percent be 0.1～20% to be selected from thiocarbamide, Benzyl Chloride, sulphur alkene, propiolic alcohol, tertiary sodium phosphate, ammonium phosphate sulfate, diammonium phosphate, triammonium phosphate, a kind of in the benzotriazole or the inhibition film-forming components that combines of two or more component arbitrarily, the blending temperature is 20～70 ℃, mixing time 2～5h.
The composition embodiment of table 2 inhibiter
| Embodiment | Inhibiter intermediate % | Solvent % | Inhibition film forming component % |
| Embodiment 19 | 10 | 80 | 10 |
| Embodiment 20 | 10 | 70 | 20 |
| Embodiment 21 | 10 | 75 | 15 |
| Embodiment 22 | 15 | 75 | 10 |
| Embodiment 23 | 15 | 80 | 5 |
| Embodiment 24 | 20 | 65 | 15 |
| Embodiment 25 | 20 | 75 | 5 |
| Embodiment 26 | 20 | 60 | 20 |
| Embodiment 27 | 25 | 55 | 20 |
| Embodiment 28 | 25 | 65 | 10 |
| Embodiment 29 | 25 | 74.5 | 0.5 |
| Embodiment 30 | 30 | 65 | 5 |
| Embodiment 31 | 30 | 67.5 | 2.5 |
| Embodiment 32 | 30 | 50 | 20 |
| Embodiment 33 | 40 | 50 | 10 |
| Embodiment 34 | 40 | 55 | 5 |
| Embodiment 35 | 40 | 59.9 | 0.1 |
| Embodiment 36 | 40 | 40 | 20 |
| Embodiment 37 | 50 | 35 | 15 |
| Embodiment 38 | 50 | 30 | 20 |
| Embodiment 39 | 50 | 45 | 5 |
| Embodiment 40 | 50 | 49.5 | 0.5 |
| Embodiment 41 | 60 | 20 | 20 |
| Embodiment 42 | 60 | 25 | 15 |
| Embodiment 43 | 60 | 30 | 10 |
| Embodiment 44 | 60 | 35 | 5 |
| Embodiment 45 | 60 | 37.5 | 2.5 |
| Embodiment 46 | 60 | 39.5 | 0.5 |
| Embodiment 47 | 60 | 39.9 | 0.1 |
| Embodiment 48 | 55 | 35 | 10 |
| Embodiment 49 | 45 | 45 | 10 |
| Embodiment 50 | 35 | 60 | 5 |
| Embodiment 51 | 30 | 69.9 | 0.1 |
3 embodiment 52～70: about the embodiment of inhibiter practical application
The described inhibiter of 30～1000 μ g/g added in 200～400 ℃ the high-temperature organic acid corrosive medium and mix.Corrosion mitigating effect performance evaluation adopts GB GB10124-86 " the even inhibition total immersion test in metallic substance laboratory method " to carry out inhibiter erosion rate corrosion inhibition rate static measurement.Used test chamber is estimated in inhibition can adopt high temperature resistant, withstand voltage, corrosion-resistant sealed vessel, and the container material can adopt stainless steel or plastics or glass etc. such as 316L, 1Cr18Ni9Ti.
Table 3 inhibiter practical application embodiment
| Embodiment | Inhibiter embodiment | Corrosive medium | Inhibiter dosage μ g/g | Temperature ℃ | Corrosion inhibition rate % | Erosion rate mm/a |
| Embodiment 52 | Embodiment 19 | Normal three acid | 30 | 200 | 90.62 | 6.26 |
| Embodiment 53 | Embodiment 19 | Subtract diacid | 300 | 300 | 91.68 | 2.06 |
| Embodiment 54 | Embodiment 21 | Subtract three acid | 550 | 400 | 97.54 | 0.61 |
| Embodiment 55 | Embodiment 19 | Furfural | 800 | 200 | 98.32 | 0.52 |
| Embodiment 56 | Embodiment 25 | Furancarboxylic acid | 1000 | 350 | 97.17 | 0.70 |
| Embodiment 57 | Embodiment 35 | Subtract tetracid | 100 | 200 | 93.25 | 5.01 |
| Embodiment 58 | Embodiment 35 | Formic acid | 400 | 300 | 90.49 | 2.33 |
| Embodiment 59 | Embodiment 33 | Stearic acid | 500 | 400 | 93.33 | 0.96 |
| Embodiment 60 | Embodiment 40 | Triacontanoic acid | 800 | 200 | 98.94 | 0.47 |
| Embodiment 61 | Embodiment 35 | Ricinolic acid | 700 | 350 | 99.01 | 0.30 |
| Embodiment 62 | Embodiment 51 | Oleic acid | 350 | 200 | 97.56 | 5.79 |
| Embodiment 63 | Embodiment 43 | Inspire confidence in your oleic acid | 600 | 300 | 93.47 | 0.59 |
| Embodiment 64 | Embodiment 28 | Normal three acid subtract diacid | 450 | 400 | 95.05 | 3.88 |
| Embodiment 65 | Embodiment 51 | Furfural+subtract diacid | 880 | 200 | 96.22 | 1.53 |
| Embodiment 66 | Embodiment 46 | Furfural+normal three acid+subtract diacid | 750 | 350 | 98.13 | 1.25 |
| Embodiment 67 | Embodiment 23 | Normal three acid+subtract diacid | 80 | 230 | 94.13 | 1.25 |
| Embodiment 68 | Embodiment 26 | Subtract tetracid | 150 | 380 | 94.86 | 1.06 |
| Embodiment 69 | Embodiment 30 | Oleic acid | 200 | 250 | 95.27 | 0.87 |
| Embodiment 70 | Embodiment 38 | Subtract diacid+subtract three acid | 250 | 240 | 96.85 | 0.71 |
Claims (5)
1, a kind of water-soluble high-temperature organic acid inhibitor, it is characterized in that: comprise by weight percentage: 10～60% inhibiter intermediate by boric acid and organic amine reaction acquisition, 20～80% methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, isopropylcarbinol, 1, the 2-propylene glycol, Pentyl alcohol, n-Heptyl alcohol, monohydroxy-alcohol or diol solvent that one or more combination of components in the n-Octanol form, 0.1～20% thiocarbamide, Benzyl Chloride, sulphur alkene, propiolic alcohol, tertiary sodium phosphate, ammonium phosphate sulfate, diammonium phosphate, triammonium phosphate, the inhibition film-forming components that one or more components in the benzotriazole combine.
2, the preparation method of a kind of water-soluble high-temperature organic acid inhibitor according to claim 1, it is characterized in that: the 1. preparation of high-temperature organic acid inhibitor intermediate: boric acid and organic amine 1: 0.5 in molar ratio～3 are put in the there-necked flask, and add 5～30% the varsol account for boric acid and organic amine gross weight, under constantly stirring, be warming up to 100～300 ℃, refluxed 2～20 hours, when the reaction mixture acid number reaches 3～20mgKOH/g, reaction finishes, and obtains the high-temperature organic acid inhibitor intermediate; After the high-temperature organic acid inhibitor intermediate that 2. will account for water-soluble high-temperature organic acid inhibitor weight percent 10～60% is cooled to 60～70 ℃, add while stirring under normal pressure that to account for the water-soluble high-temperature organic acid inhibitor weight percent be 20～80% methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, isopropylcarbinol, 1, the 2-propylene glycol, Pentyl alcohol, n-Heptyl alcohol, monohydroxy-alcohol or diol solvent that one or more combination of components in the n-Octanol form, and to account for the water-soluble high-temperature organic acid inhibitor weight percent be 0.1～20% to be selected from thiocarbamide, Benzyl Chloride, sulphur alkene, propiolic alcohol, tertiary sodium phosphate, ammonium phosphate sulfate, diammonium phosphate, triammonium phosphate, the inhibition film-forming components that one or more components in the benzotriazole combine, by the blending temperature is 20～70 ℃, time is that the mode of 2～5h is concocted, and can make.
3, the preparation method of water-soluble high-temperature organic acid inhibitor according to claim 2, it is characterized in that described organic amine is quadrol, N-hydroxyethyl-ethylenediamine, N-methyl, N-diethanolamine, methyl tertiary amine, Trimethylamine 99, diethanolamine, trolamine, N-methyl, N-ethylol amine, N-ethyl, N-ethylol amine, N-butyl, a kind of or any two or more component in the N-ethylol amine combines.
4, the preparation method of water-soluble high-temperature organic acid inhibitor according to claim 2 is characterized in that: described varsol is the mixture that one or more components in toluene, dimethylbenzene, sherwood oil or the gasoline combine.
5, the using method of a kind of water-soluble high-temperature organic acid inhibitor according to claim 1, it is characterized in that the water-soluble high-temperature organic acid inhibitor that will account for 30～1000 μ g/g of 200～400 ℃ of high-temperature organic acid corrosive medium weight adds in the above-mentioned corrosive medium, thorough mixing is even.
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