CN102559263B - High temperature corrosion inhibitor for oil refining device - Google Patents
High temperature corrosion inhibitor for oil refining device Download PDFInfo
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- CN102559263B CN102559263B CN201110413636.5A CN201110413636A CN102559263B CN 102559263 B CN102559263 B CN 102559263B CN 201110413636 A CN201110413636 A CN 201110413636A CN 102559263 B CN102559263 B CN 102559263B
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- 238000005260 corrosion Methods 0.000 title claims abstract description 96
- 230000007797 corrosion Effects 0.000 title claims abstract description 93
- 239000003112 inhibitor Substances 0.000 title claims abstract description 44
- 238000007670 refining Methods 0.000 title claims abstract description 10
- -1 alkyl dianhydride Chemical compound 0.000 claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 36
- 239000011593 sulfur Substances 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 15
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000768 polyamine Polymers 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 229960002317 succinimide Drugs 0.000 claims abstract description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 67
- 239000002253 acid Substances 0.000 claims description 38
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002131 composite material Substances 0.000 claims description 9
- 239000008096 xylene Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 8
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 6
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 claims description 6
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 150000004291 polyenes Chemical class 0.000 claims description 6
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- DXYYSGDWQCSKKO-UHFFFAOYSA-N 2-methylbenzothiazole Chemical compound C1=CC=C2SC(C)=NC2=C1 DXYYSGDWQCSKKO-UHFFFAOYSA-N 0.000 claims description 5
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001993 dienes Chemical class 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 3
- GBRSPKXOFRTAHS-UHFFFAOYSA-N 5-(4-nitrophenyl)-1,2-oxazole-3-carboxylic acid Chemical compound O1N=C(C(=O)O)C=C1C1=CC=C([N+]([O-])=O)C=C1 GBRSPKXOFRTAHS-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000002636 imidazolinyl group Chemical group 0.000 claims description 3
- KCRLWVVFAVLSAP-UHFFFAOYSA-N octyl dihydrogen phosphite Chemical compound CCCCCCCCOP(O)O KCRLWVVFAVLSAP-UHFFFAOYSA-N 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- FSLSJTZWDATVTK-UHFFFAOYSA-N tris(6-methylheptyl) phosphate Chemical compound CC(C)CCCCCOP(=O)(OCCCCCC(C)C)OCCCCCC(C)C FSLSJTZWDATVTK-UHFFFAOYSA-N 0.000 claims description 3
- CXUXSVRYIFBRSZ-UHFFFAOYSA-N 2-cyclohexyl-1,3-benzothiazole Chemical compound C1CCCCC1C1=NC2=CC=CC=C2S1 CXUXSVRYIFBRSZ-UHFFFAOYSA-N 0.000 claims description 2
- CVULGJIRGZVJHQ-UHFFFAOYSA-N 2-ethylbenzothiazole Chemical compound C1=CC=C2SC(CC)=NC2=C1 CVULGJIRGZVJHQ-UHFFFAOYSA-N 0.000 claims description 2
- XBHOUXSGHYZCNH-UHFFFAOYSA-N 2-phenyl-1,3-benzothiazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2S1 XBHOUXSGHYZCNH-UHFFFAOYSA-N 0.000 claims description 2
- LWYAUHJRUCQFCX-UHFFFAOYSA-N 4-dodecoxy-4-oxobutanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCC(O)=O LWYAUHJRUCQFCX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002367 Polyisobutene Polymers 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 3
- 230000000630 rising effect Effects 0.000 abstract 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 17
- 239000010779 crude oil Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000005764 inhibitory process Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910000975 Carbon steel Inorganic materials 0.000 description 7
- 239000010962 carbon steel Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000000116 mitigating effect Effects 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- 0 C*(C)*CN=CC Chemical compound C*(C)*CN=CC 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VZWOXDYRBDIHMA-UHFFFAOYSA-N Cc1ncc[s]1 Chemical compound Cc1ncc[s]1 VZWOXDYRBDIHMA-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006518 acidic stress Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 125000005331 diazinyl group Chemical group N1=NC(=CC=C1)* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Lubricants (AREA)
Abstract
The invention relates to a high temperature corrosion inhibitor for an oil refining device. The high temperature corrosion inhibitor needs to overcome the shortcoming that an adsorption film is easy to fall off, solves the problem that the traditional high temperature corrosion inhibitor is lower in the using temperature, leads the applicable temperature of a product to be higher and has better effect. The high temperature corrosion inhibitor is prepared by adopting the following steps of: (1) firstly dissolving a part of alkyl diacid or alkyl dianhydride in an aromatic hydrocarbon solvent, stirring and adding a thiazole compound, rising temperature, then dropwise adding polyethylene polyamine, rising temperature, keep temperature constant after dewatering and removing the aromatic hydrocarbon solvent, adding the aromatic hydrocarbon solvent and residual alkyl diacid or alkyl dianhydride again, and reacting to obtain a nitrogenous and sulfur containing polymer solution; and (2) compounding and uniformly stirring 20-40 parts by weight of nitrogenous and sulfur containing polymer solution (based on 20-40 parts by weight of nitrogenous and sulfur containing polymer) prepared in the step (1), 10-30 parts by weight of (phosphite) phosphate ester compound, 0-5 parts by weight of alkenyl succinimide compound and 70-25 parts by weight of aromatic hydrocarbon solvent.
Description
Technical field
The invention belongs to the inhibition field of metallic substance, specifically a kind of for petroleum refining process, temperature, higher than 200 ℃, especially has the dangerous lip-deep high-temperature corrosion inhibitor of e-quipment and pipe of corrosion and the preparation method of this inhibiter higher than 320 ℃.
Background technology
In recent years, along with China is to the exploitation of peracid high-sulfur crude oil and utilization, processing crude oil with high acid value refinery temperature is also more and more serious at the corrosion condition of more than 230 ℃ high temperature position carbon steel equipments.The corrosion of oil refining apparatus high temperature position equipment is mainly naphthenic acid corrosion, will produce strong corrosion by metallic substance, and in the crude oil having at present, acid number has reached 6～10mgKOH/g under the crude oil high temperature of acid number more than 0.5mgKOH/g.In high-temperature high-flow rate district, more than the corrosion of carbon steel equipment has reached 20mm/a.When in crude oil, sulphur content is greater than 1% in addition, can there is corrosion synergy in sulphur and naphthenic acid, causes corrosion aggravation greatly.Because the oil refining apparatus that causes of corrosion stops production, stop work, firing accident happens occasionally, serious harm the safety in production of refinery.
The temperature range of naphthenic acid corrosion is 230～400 ℃, occurs first peak of naphthenic acid corrosion in the time of 270～280 ℃, at 340～350 ℃, occurs second corrosion peak; At 400 ℃, do not observe above naphthenic acid corrosion, because now naphthenic acid decomposes completely.
The method of controlling at present oil refining apparatus high temperature position equipment corrosion is mainly to reduce acid value for crude oil and sulphur content, the anti-corrosion grade of raising equipment and the high-temperature corrosion inhibitor of annotating.The method that reduces acid value for crude oil and sulphur content is mainly by being in harmonious proportion, neutralizing, extracting, changing the acid number that the methods such as naphthenic acid form reduce crude oil, adopts the methods such as hydrogenating desulfurization, solvent desulfurization, biological desulphurization to remove the S-contained substance in crude oil.For peracid high-sulfur crude oil, need to be in harmonious proportion with the low sour sweet crude oil of several times of amounts, obvious this method can not solve naphthenic acid corrosion problem completely.Adopt the material that anti-corrosion grade is high to have certain resistant function to naphthenic acid corrosion, but the materials such as 1Cr18Ni9Ti are expensive, are about 5～10 times of carbon steel.In addition, austenitic stainless steel is quite responsive to hydrogen embrittlement and polythionic acid stress corrosion cracking, and the device downtime likely causes stress corrosion cracking.It is little that filling high-temperature corrosion inhibitor method has investment, and the advantage of easy to use and flexible, does not need to set up complicated equipment, and can determine according to corrosion condition filling position and the consumption of inhibiter.
The domestic patent about high temperature inhibitor for oil refining apparatus is less.CN1069529A discloses a kind of high-remp. oil phase corrosion inhibitor, is a kind of organic film-forming corrosion inhibitor being composited by alkyl acid phosphate ester cpds and alkyl diazine ring system compounds.Dynamic corrosion test result shows, at corrosion temperature, is 280 ℃, and Medium Oil is Karamay viscous crude oil (acid number is 4.87mgKOH/g), and density of corrosion inhibitor is under the condition of 50 μ g/g, to 20
#the corrosion inhibition rate of carbon steel is 86.7%.CN1869287A discloses a kind of high-temperature corrosion inhibitor, by thiophosphatephosphorothioate compounds and imidazolines, is composited.Corrosion test result shows, in temperature, is 260～270 ℃, and corrosive medium acid number is that 5.0mgKOH/g, sulphur content are 450 μ g/g, and density of corrosion inhibitor is 100 μ g/g, under the condition that the corrosion test time is 6h, to 20
#the corrosion inhibition rate of carbon steel is 96.5%.CN101440493A discloses a kind of high-temperature corrosion inhibitor for atmospheric and vacuum distillation unit, fatty acid amide, organic amine, sulfonated alkylphenol, organosulfur phosphorus compound, phosphoric acid ester and heavy aromatics, consists of.Corrosion test result shows, in temperature, is 270 ± 5 ℃, and corrosive medium acid number is 5.0mgKOH/g, under the condition that the corrosion test time is 12h, to 20
#the corrosion inhibition rate of carbon steel is 945%.
External more about the patent of high-temperature corrosion inhibitor.US4941994 discloses a kind of high-temperature corrosion inhibitor, is the mixture of a kind of alkylphosphonic acid carboxylic acid ester compound or alkylphosphonic acid carboxylic acid ester compound and Thiazoling type compound.This inhibiter large usage quantity, the acid-containing hydrocarbon oil of controlling acid number 1.5mgKOH/g is to the erosion rate of carbon steel equipment below O.5mm/a, and more than must injecting inhibiter 1000 μ g/g, cost of use is high.US5863415 discloses a kind of alkyl phosphate type high temp inhibiter, and in the time of 300 ℃, addition is 2500 μ g/g, and under the condition that Medium Oil total acid value is 4.2mgKOH/g, corrosion inhibition rate can reach 87.7%.Exxon company discloses a class organic polysulfide compound high-temperature corrosion inhibitor in EP0607640, and its best corrosion mitigating effect is in the time of 204 ℃, and under the addition condition of 1000 μ g/g, corrosion inhibition rate reaches 80%.
From current published patent, the evaluation of high-temperature corrosion inhibitor effect is mainly concentrated on below 300 ℃, but from oil refining process, often, at the bottom of the tower of vacuum distillation tower, transfer line, vaporization section etc., temperature is all more than 340 ℃, in second corrosion peak of naphthenic acid, corrosion phenomenon is serious, needs the inhibiter that use temperature is higher to prevent the corrosion in these regions.
Summary of the invention
The technical issues that need to address of the present invention are, have overcome the shortcoming that high-temperature corrosion inhibitor adsorption film easily comes off, use temperature is lower, and product Applicable temperature is higher, better effects if.
High-temperature corrosion inhibitor of the present invention is a kind of organic film-forming corrosion inhibitor, as follows:
1) preparation of nitrogenous sulfur-bearing polymer:
The alkyl acid of 70～90% total consumptions or alkyl acid acid anhydride are dissolved in aromatic hydrocarbon solvent, under agitation condition, slowly add thiazole compound, after thiazole compound all adds, be warming up to 60～160 ℃ of reactions of required temperature of reaction 1～3 hour, then be added dropwise to polyethylene polyamine, be warming up to 100～250 ℃, after the de-aromatic hydrocarbon solvent of dehydration, constant temperature is 3～7 hours, the alkyl acid or the alkyl acid acid anhydride that add again aromatic hydrocarbon solvent and residual content, react 1～3 hour, obtain nitrogenous sulfur-bearing polymer solution; This polymer solution normally general structure is the different mixture of the polymerization degree of formula (1), can be directly used in the preparation of high-temperature corrosion inhibitor, does not need desolvation.
(1)，
In formula (1), m is 1～20 integer (being preferably 2～10 integer); R is C
8～C
30alkyl or alkyl derivative (be preferably C
12～C
24alkyl or alkyl derivative); X is N atom or O atom; R
1be the functional group with thiazole structure, its structural formula is
or
r
2be the functional group with imidazoline structure, its general structure is formula (2):
In formula (2), n is 1～4 integer;
Described alkyl acid and/or alkyl acid acid anhydride select one or more the mixture in white dodecyl succinate, dodecyl succinic anhydride, tetradecyl succsinic acid, tetradecyl succinyl oxide, hexadecyl succsinic acid, hexadecyl succinyl oxide, octadecyl succsinic acid, octadecyl succinyl oxide, and total consumption is 20～50 weight parts;
Described thiazole compound selects one or more the mixture in white benzothiazole, methylbenzothiazole, ethyl benzothiazole, cyclohexyl benzo thiazole, phenyl benzothiazole, hydroxybenzothiazole, mercaptobenzothiazole, benzothiazolyl mercaptan, aminobenzothiazole, and consumption is 2～8 weight parts;
The general structure of described polyethylene polyamine is H
2n (CH
2cH
2nH)
nh, wherein n is 2～6 positive integers, selects one or more mixtures (being preferably one or more mixtures in diethylenetriamine, triethylene tetramine, tetraethylene pentamine) wherein, consumption is 10～25 weight parts.
Described aromatic hydrocarbon solvent is selected from benzene,toluene,xylene and/or heavy aromatics kind solvent oil (being preferably dimethylbenzene and/or heavy aromatics kind solvent oil), and consumption is 68～17 weight parts;
2) preparation of high-temperature corrosion inhibitor:
High-temperature corrosion inhibitor by nitrogenous sulfur-bearing polymer and phosphite ester compound and/or phosphate compounds, divinyl imine compound, aromatic hydrocarbon solvent is composite makes.
The nitrogenous sulfur-bearing polymer solution that upper step is made joins in aromatic hydrocarbon solvent, add again phosphate compounds or phosphite ester compound, allyl butyrate diimide compounds to carry out composite, stir, obtain high-temperature corrosion inhibitor provided by the invention, the consumption of nitrogenous sulfur-bearing polymer solution be take nitrogenous sulfur-bearing polymer and is converted as 20～40 weight parts;
Described phosphate compounds and/or phosphite ester compound are selected from one or more the mixture (being preferably diisooctyl phenyl phosphite, tricresyl phosphite monooctyl ester and/or triisooctyl phosphate) in diisooctyl phenyl phosphite, the different monooctyl ester of phosphorous acid hexichol one, triphenyl phosphite, tricresyl phosphite monooctyl ester, etherophosphoric acid, tributyl phosphate, triisooctyl phosphate, triphenylphosphate, and consumption is 10～30 weight parts;
Described allyl butyrate diimide compounds is selected from one or more the mixture (being preferably diene base succimide and/or polyene-based succimide) in mono alkenyl succimide, diene base succimide, polyene-based succimide, low nitrogen polyisobutene succinimide, high nitrogen polyisobutenyl imide, and consumption is 0～5 weight part;
Described aromatic hydrocarbon solvent is selected from benzene,toluene,xylene and/or heavy aromatics kind solvent oil (being preferably dimethylbenzene and/or heavy aromatics kind solvent oil), and consumption is 70～25 weight parts.
High-temperature corrosion inhibitor provided by the invention, in nitrogenous sulfur-bearing polymer molecule wherein, contain a plurality of can metallic surface thiazole structure and the imidazoline structure of absorption, can make inhibitor molecular be adsorbed on securely metallic surface, overcome adsorption film and held caducous shortcoming, (Asia) phosphate compounds can be adsorbed on the gap of nitrogenous sulfur-bearing polymer adsorption film simultaneously, make whole adsorption film finer and close, thereby greatly improved the corrosion mitigating effect of inhibiter.It is worth mentioning that, high-temperature corrosion inhibitor provided by the invention still has good corrosion mitigating effect under the hot conditions of 360 ℃, can prevent the equipment corrosion in second corrosion peak of naphthenic acid.In addition, high-temperature corrosion inhibitor stable performance provided by the invention, raw material is cheap and easy to get, and cost is lower, is conducive to apply at oil refining apparatus.
Embodiment
Below by implementing just to illustrate high-temperature corrosion inhibitor of the present invention and preparation method thereof, but embodiment does not limit the scope of the invention.
Embodiment 1:
The preparation of nitrogenous sulfur-bearing polymer---85 grams of hexadecyl succinyl oxides and 100 grams of dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, water trap and condenser are housed.Spending whipping appts is opened water of condensation simultaneously, more slowly adds 30 grams of hydroxybenzothiazoles, is warming up to dimethylbenzene and starts to reflux, and reacts 1 hour.Then be added dropwise to 60 grams of triethylene tetramines, react after 1 hour, be warmed up to 220 ℃, dehydration, desolventizing, is cooled to 100 ℃ after constant temperature 5h.Add again 200 grams of dimethylbenzene and 35 grams of hexadecyl succinyl oxides, be warming up to dimethylbenzene and start to reflux, react the cooling xylene solution that obtains nitrogenous sulfur-bearing polymer 2 hours.
The preparation of high-temperature corrosion inhibitor---the nitrogenous sulfur-bearing polymer solution that 70 grams of upper steps are prepared joins in 20 grams of dimethylbenzene, dissolve, then it is composite to add 10 grams of triphenyl phosphites to carry out, and obtains high-temperature corrosion inhibitor provided by the invention.
Embodiment 2:
The preparation of nitrogenous sulfur-bearing polymer---98 grams of tetradecyl succinyl oxides and 100 grams of dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, water trap and condenser are housed.Spending whipping appts is opened water of condensation simultaneously, more slowly adds 18 grams of hydroxybenzothiazoles, is warming up to dimethylbenzene and starts to reflux, and reacts 2 hours.Then be added dropwise to 72 grams of tetraethylene pentamine, react after 1 hour, be warmed up to 220 ℃, dehydration, desolventizing, is cooled to 100 ℃ after constant temperature 5h.Add again 200 grams of dimethylbenzene and 22 grams of tetradecyl succinyl oxides, be warming up to dimethylbenzene and start to reflux, react the cooling xylene solution that obtains nitrogenous sulfur-bearing polymer 2 hours.
The preparation of high-temperature corrosion inhibitor---the nitrogenous sulfur-bearing polymer solution that 58 grams of upper steps are prepared joins in 20 grams of dimethylbenzene, dissolve, add again the mixture of 20 grams of triisooctyl phosphates, 2 grams of diene base succimides to carry out composite, obtain high-temperature corrosion inhibitor provided by the invention.
Embodiment 3:
The preparation of nitrogenous sulfur-bearing polymer---105 grams of hexadecyl succsinic acids and 100 grams of dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, water trap and condenser are housed.Spending whipping appts is opened water of condensation simultaneously, more slowly adds 10 grams of aminobenzothiazoles, is warming up to dimethylbenzene and starts to reflux, and reacts 3 hours.Then be added dropwise to 80 grams of tetraethylene pentamine, react after 1 hour, be warmed up to 220 ℃, dehydration, desolventizing, is cooled to 100 ℃ after constant temperature 5h.Add again 200 grams of dimethylbenzene and 15 grams of hexadecyl succsinic acids, be warming up to dimethylbenzene and start to reflux, react the cooling xylene solution that obtains nitrogenous sulfur-bearing polymer 2 hours.
The preparation of high-temperature corrosion inhibitor---the nitrogenous sulfur-bearing polymer solution that 46 grams of upper steps are prepared joins in 20 grams of dimethylbenzene, dissolve, add again 30 grams of different monooctyl esters of phosphorous acid hexichol one, 4 grams of polyene-based succimides to carry out composite, obtain high-temperature corrosion inhibitor provided by the invention.
Embodiment 4:
The preparation of nitrogenous sulfur-bearing polymer---85 grams of dodecyl succinic anhydrides and 100 grams of dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, water trap and condenser are housed.Spending whipping appts is opened water of condensation simultaneously, more slowly adds 30 grams of aminobenzothiazoles, is warming up to dimethylbenzene and starts to reflux, and reacts 1 hour.Then be added dropwise to 60 grams of triethylene tetramines, react after 1 hour, be warmed up to 220 ℃, dehydration, desolventizing, is cooled to 100 ℃ after constant temperature 5h.Add again 200 grammes per square metre aromatic solvent naphthas and 35 grams of dodecyl succinic anhydrides, be warming up to solvent refluxing, react 2 hours, coolingly obtain nitrogenous sulfur-bearing polymer solution.
The preparation of high-temperature corrosion inhibitor---the nitrogenous sulfur-bearing polymer solution that 70 grams of upper steps are prepared joins in 20 grammes per square metre aromatic solvent naphthas, dissolve, then it is composite to add 10 grams of tributyl phosphates to carry out, and obtains high-temperature corrosion inhibitor provided by the invention.
Embodiment 5:
The preparation of nitrogenous sulfur-bearing polymer---95 grams of tetradecyl succinyl oxides and 100 grams of dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, water trap and condenser are housed.Spending whipping appts is opened water of condensation simultaneously, more slowly adds 18 grams of aminobenzothiazoles, is warming up to dimethylbenzene and starts to reflux, and reacts 2 hours.Then be added dropwise to 72 grams of triethylene tetramines, react after 1 hour, be warmed up to 220 ℃, dehydration, desolventizing, is cooled to 100 ℃ after constant temperature 5h.Add again 200 grams of dimethylbenzene and 25 grams of tetradecyl succinyl oxides, be warming up to dimethylbenzene and start to reflux, react the cooling xylene solution that obtains nitrogenous sulfur-bearing polymer 2 hours.
The preparation of high-temperature corrosion inhibitor---the nitrogenous sulfur-bearing polymer solution that 57 grams of upper steps are prepared joins in 20 grams of dimethylbenzene, dissolve, add again the mixture of 20 grams of triisooctyl phosphates, 3 grams of polyene-based succimides to carry out composite, obtain high-temperature corrosion inhibitor provided by the invention.
Embodiment 6:
The preparation of nitrogenous sulfur-bearing polymer---105 grams of hexadecyl succinyl oxides and 100 grams of dimethylbenzene are put into the 500ml four-hole boiling flask that agitator, thermometer, water trap and condenser are housed.Spending whipping appts is opened water of condensation simultaneously, more slowly adds 10 grams of aminobenzothiazoles, is warming up to dimethylbenzene and starts to reflux, and reacts 3 hours.Then be added dropwise to 80 gram of five ethene hexamine, react after 1 hour, be warmed up to 220 ℃, dehydration, desolventizing, is cooled to 100 ℃ after constant temperature 5h.Add again 200 grams of dimethylbenzene and 15 grams of hexadecyl succinyl oxides, be warming up to dimethylbenzene and start to reflux, react the cooling xylene solution that obtains nitrogenous sulfur-bearing polymer 2 hours.
The preparation of high-temperature corrosion inhibitor---the nitrogenous sulfur-bearing polymer solution that 45 grams of upper steps are prepared joins in 20 grams of dimethylbenzene, dissolve, add again 30 grams of triphenyl phosphites, 5 grams of polyene-based succimides to carry out composite, obtain high-temperature corrosion inhibitor provided by the invention.
The high-temperature corrosion inhibitor that adopts weight-loss method Evaluation operation example 1～6 to obtain.
Autoclave: 1000ml, inwall is 316L stainless steel.
Corrosive medium: will subtract third fractional oil with commodity naphthenic acid be adjusted to acid number be 12mgKOH/g as corrosive medium, each experimental measuring is 600mL.
Corrosion coupon: III type standard corrosion coupon, material is 20# steel.First with sherwood oil, soak wiping, with dehydrated alcohol, clean and soak 24h afterwards, after taking-up, with filter paper, blot and put moisture eliminator and save backup
Test temperature: 280 ℃, 360 ℃.
Agitator speed: 500 revs/min.
Test period: 6 hours.
Inhibiter filling rate: 500 μ g/g.
Evaluation method: the weight before and after the test of accurate weighing corrosion coupon, accurately to 0.0001 gram, according to the weight loss corrosion inhibition rate of test piece.Corrosion inhibition rate is calculated as follows:
In formula:
η---corrosion inhibition rate (%);
Δ W
1---add the corrosion weight loss numerical value of test piece under inhibiter condition, unit is gram (g);
Δ W
0---the corrosion weight loss numerical value of test piece under blank condition, unit is gram (g).
Calculation result represents 2 significant digits.
The evaluation result of high-temperature corrosion inhibitor is in Table 1.
The evaluation result of table 1 high-temperature corrosion inhibitor
Claims (1)
1. a high temperature corrosion inhibitor for oil refining device, is characterized in that as follows:
1) preparation of nitrogenous sulfur-bearing polymer:
The alkyl acid of 70～90% total consumptions or alkyl acid acid anhydride are dissolved in aromatic hydrocarbon solvent, under agitation condition, slowly add thiazole compound, after thiazole compound all adds, be warming up to 60～160 ℃ of reactions of required temperature of reaction 1～3 hour, then be added dropwise to polyethylene polyamine, be warming up to 100～250 ℃, after the de-aromatic hydrocarbon solvent of dehydration, constant temperature 3～7 hours, the alkyl acid or the alkyl acid acid anhydride that add again aromatic hydrocarbon solvent and residual content, react 1～3 hour, obtain nitrogenous sulfur-bearing polymer solution, this polymer solution is that general structure is the different mixture of the polymerization degree of formula (1):
In formula (1), m is 1～20 integer; R is C
8～C
30alkyl or alkyl derivative; X is N atom or O atom; R
1be the functional group with thiazole structure, its structural formula is
r
2be the functional group with imidazoline structure, its general structure is formula (2):
In formula (2), n is 1～4 integer;
Described alkyl acid and/or alkyl acid acid anhydride are selected from one or more the mixture in dodecyl succinate, dodecyl succinic anhydride, tetradecyl succsinic acid, tetradecyl succinyl oxide, hexadecyl succsinic acid, hexadecyl succinyl oxide, octadecyl succsinic acid, octadecyl succinyl oxide, and total consumption is 20～50 weight parts;
Described thiazole compound is selected from one or more the mixture in benzothiazole, methylbenzothiazole, ethyl benzothiazole, cyclohexyl benzo thiazole, phenyl benzothiazole, hydroxybenzothiazole, mercaptobenzothiazole, aminobenzothiazole, and consumption is 2～8 weight parts;
The general structure of described polyethylene polyamine is H
2n (CH
2cH
2nH)
nh, wherein n is 2～6 positive integers, selects one or more mixtures wherein, consumption is 10～25 weight parts;
Described aromatic hydrocarbon solvent is selected from benzene,toluene,xylene and/or heavy aromatics kind solvent oil,
be 68～17 weight parts;
2) preparation of high-temperature corrosion inhibitor:
The nitrogenous sulfur-bearing polymer solution that upper step is made joins in aromatic hydrocarbon solvent, add again phosphate compounds or phosphite ester compound, allyl butyrate diimide compounds to carry out composite, stir, obtain high-temperature corrosion inhibitor provided by the invention, the consumption of nitrogenous sulfur-bearing polymer solution be take nitrogenous sulfur-bearing polymer and is converted as 20～40 weight parts;
Described phosphate compounds and/or phosphite ester compound are selected from one or more the mixture in diisooctyl phenyl phosphite, the different monooctyl ester of phosphorous acid hexichol one, triphenyl phosphite, tricresyl phosphite monooctyl ester, etherophosphoric acid, tributyl phosphate, triisooctyl phosphate, triphenylphosphate, and consumption is 10～30 weight parts;
Described allyl butyrate diimide compounds is selected from one or more the mixture in mono alkenyl succimide, diene base succimide, polyene-based succimide, low nitrogen polyisobutene succinimide, high nitrogen polyisobutenyl imide, and consumption is 0～5 weight part;
Described aromatic hydrocarbon solvent is selected from benzene,toluene,xylene and/or heavy aromatics kind solvent oil,
be 70～25 weight parts.
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