CN105297029A - Crude oil decalcifying agent matched corrosion inhibitor and preparation method thereof - Google Patents
Crude oil decalcifying agent matched corrosion inhibitor and preparation method thereof Download PDFInfo
- Publication number
- CN105297029A CN105297029A CN201510810108.1A CN201510810108A CN105297029A CN 105297029 A CN105297029 A CN 105297029A CN 201510810108 A CN201510810108 A CN 201510810108A CN 105297029 A CN105297029 A CN 105297029A
- Authority
- CN
- China
- Prior art keywords
- crude oil
- decalcifying agent
- oil decalcifying
- triazole
- corrosion inhibitor
- 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.)
- Granted
Links
- 0 **1c2ccccc2**1 Chemical compound **1c2ccccc2**1 0.000 description 3
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Lubricants (AREA)
Abstract
The invention provides a crude oil decalcifying agent matched corrosion inhibitor. The crude oil decalcifying agent matched corrosion inhibitor is prepared from 30-50 wet% of thiourea-triazole-pyridine compounds, 0.5-2 wt% of a non-ionic surface active agent, 5-10 wt% of low-molecular-weight alcohol, 0.5-2 wt% of an inorganic corrosion inhibitor and 30-60 wt% of water. The invention further relates to a preparation method of the crude oil decalcifying agent matched corrosion inhibitor. The preparation method includes the steps that ethyl-3-chloro propionate and methylbenzotriazole react to generate an intermediate with potassium carbonate as catalysts and with acetone as a solvent; then, the intermediate reacts with hydrazine hydrate to generate methylbenzotriazole hydrazide with ethyl alcohol as a solvent; potassium thiocyanate and 2-pyridinecarboxylicacid react with methyl benzotriazole hydrazide to generate thiourea-triazole-pyridine compounds with ethyl acetate as a solvent; and finally, thiourea-triazole-pyridine compounds, a non-ionic surface active agent, low-molecular-weight alcohol, inorganic corrosion inhibitor and water are stirred for 1-2 hours at a temperature of 30-50 DEG C, and then cooling, filtering and solid impurity removing are conducted to obtain the crude oil decalcifying agent matched corrosion inhibitor. By means of the crude oil decalcifying agent matched corrosion inhibitor, corrosivity of a crude oil decalcifying agent can be effectively controlled.
Description
Technical field:
The invention belongs to technical field of metal corrosion protection, relate to the supporting inhibiter of a kind of crude oil decalcifying agent, this inhibiter effectively can control crude oil decalcifying agent in the corrosion of desalting in oil refinery process section to hardware and pipeline.
Background technology:
Crude oil decalcifying agent be a kind of can the Petroleum Refining Additives of the metallic impurity such as efficient removal Calcium in Crude Oil.Crude oil decalcifying agent is applied in desalting in oil refinery device, forms water miscible compound, make the metal ions such as calcium ion transfer to aqueous phase from oil phase with the mode of chelating and displacement and Calcium in Crude Oil ion, discharging, reaching demetalization object with cutting water.Filling crude oil decalcifying agent can make crude oil remove the metallic impurity such as most calcium before entering atmospheric and vacuum distillation unit, solve the refinery's downstream unit fouling, the corrosion phenomenon that cause because metal content in crude oil is high serious, poisoning of catalyst even permanent deactivation in the operation such as hydrocracking, catalytic cracking, and refinery coke product ash content such as to exceed standard at the series of problems, for oil refining enterprise adds significant economic benefit.
But crude oil decalcifying agent mostly is strongly-acid material, can cause serious corrosion to desalting in oil refinery process section associated metal equipment and pipeline in its use procedure, the long-term stability affecting refinery is run.
Carry out the research of many crude oil decalcifying agent aspects in recent years both at home and abroad, but but rarely have the research about the supporting inhibiter of crude oil decalcifying agent to report.Therefore, need a kind of corrodibility that effectively can control crude oil decalcifying agent badly, do not affect the inhibiter of crude oil decalcifying agent use properties simultaneously.
Summary of the invention:
For the deficiencies in the prior art, the invention provides a kind of supporting inhibiter of crude oil decalcifying agent being main component with Novel thiourea-triazole-pyridine compounds, a kind of method preparing the supporting inhibiter of crude oil decalcifying agent is provided simultaneously.
1. the supporting inhibiter of crude oil decalcifying agent:
The supporting inhibiter of a kind of crude oil decalcifying agent provided by the invention, it is made up of following component (weight ratio):
Thiocarbamide-triazole-pyridine compounds 30 ~ 50wt%, nonionogenic tenside 0.5 ~ 2wt%, low molecule alcohols 5 ~ 10wt%, inorganic inhibitor 0.5 ~ 2wt%, water 30 ~ 60wt%.
Thiocarbamide-triazole-pyridine compounds has the structural formula of lower formula I:
Nonionogenic tenside can be that a kind of material in paregal O-20, peregal O-25, paregal O-30 and peregal O-35 is formed, and is good with peregal O-25.
Low molecule alcohols can be that in propiolic alcohol, glycerol, Virahol, ethylene glycol, a kind of material is formed, and is good with Virahol.
Inorganic inhibitor can potassiumiodide, potassium sulfocyanate, Sodium orthomolybdate, a kind of material is formed in sodium wolframate, is good with potassiumiodide.
2. the preparation method of the supporting inhibiter of crude oil decalcifying agent:
Preparation method is divided into four steps:
(1) take salt of wormwood as catalysts, acetone is reaction solvent, the intermediate generating and there is lower formula II structure is reacted with 3-chloropropionate and methyl benzotriazazole, wherein the mol ratio of salt of wormwood, 3-chloropropionate and methyl benzotriazazole is 1:1:1, temperature of reaction 60 ~ 80 DEG C, 10 ~ 12 hours reaction times;
(2) take ethanol as reaction solvent, the methyl benzotriazazole propionyl hydrazine generating and there is lower formula III structure is reacted with intermediate and hydrazine hydrate, wherein the mol ratio of intermediate and hydrazine hydrate is 1:1, temperature of reaction 60 ~ 80 DEG C, 10 ~ 12 hours reaction times;
(3) take ethyl acetate as reaction solvent, thiocarbamide-triazole-the pyridine compounds with lower formula I structure is generated with potassium sulfocyanate, 2-pyridinecarboxylic chloride and methyl benzotriazazole propionyl hydrazine reaction, wherein the mol ratio of potassium sulfocyanate, 2-pyridinecarboxylic chloride and methyl benzotriazazole propionyl hydrazine is 1:1:0.8, temperature of reaction 60 ~ 80 DEG C, 2 ~ 3 hours reaction times;
(4) by following weight percents, thiocarbamide-triazole-pyridine compounds, nonionogenic tenside, low molecule alcohols, inorganic inhibitor and water are mixed, prepare the supporting inhibiter of crude oil decalcifying agent, wherein thiocarbamide-triazole-pyridine compounds 30 ~ 50wt%, nonionogenic tenside 0.5 ~ 2wt%, low molecule alcohols 5 ~ 10wt%, inorganic inhibitor 0.5 ~ 2wt%, water 30 ~ 60wt%; By above each component 30 ~ 50 DEG C, stir 1 ~ 2 hour under normal pressure, stirring velocity 80 ~ 100r/min, is cooled to normal temperature afterwards, by filtering and removing solid impurity, just obtains product to be prepared.
Crude oil decalcifying agent provided by the invention supporting inhibiter corrosion mitigating effect is remarkable, when carrying out corrosion test under industry standard " technical requirements of Q/SH0202-2008 crude oil decalcifying agent " defined terms, can the erosion rate of crude oil decalcifying agent be controlled at below 0.075mm/a, obviously be better than the technical indicator that crude oil decalcifying agent erosion rate that industry standard specifies is not more than 1mm/a.Meanwhile, after adding the supporting inhibiter of crude oil decalcifying agent provided by the invention, the decalcity of crude oil decalcifying agent is not adversely affected, and decalcification rate is stabilized in more than 80%, meets the requirement of industry standard.
Embodiment:
1. the preparation of the supporting inhibiter of crude oil decalcifying agent:
(1) in the 250mL four-hole boiling flask that agitator, reflux condensing tube are housed, 0.15mol methyl benzotriazazole, 0.15mol chloropropionate, 160mL reaction solvent acetone and 0.15mol catalysts salt of wormwood is added, reflux at 80 DEG C, react after 12 hours, to product suction filtration, filtrate decompression distillation obtains the intermediate with lower formula II structure.
(2) in the 250mL four-hole boiling flask that agitator, reflux condensing tube are housed, 0.15mol hydrazine hydrate, 0.15mol intermediate (II) and 100mL ethanol is added, after at 80 DEG C, heated and stirred refluxes 12 hours, reaction solution is distilled, steam about 60mL liquid, namely debris is cooled to room temperature has solid to separate out, suction filtration, uses washing with alcohol.Dry, weigh.Obtain the methyl benzotriazazole propionyl hydrazine solid of the white with lower formula III structure.
(3) under drying conditions, the ethyl acetate solution containing 0.015mol potassium sulfocyanate (drying) is added in 250mL four-hole boiling flask, slowly 0.015mol2-pyridinecarboxylic chloride is dripped wherein while stirring at 60 DEG C, add rear continuation stirring reaction 2h, filter, the Repone K that removing generates.Add 0.012mol methyl benzotriazazole propionyl hydrazine solid (III) in filtrate, back flow reaction 4h, thin-layer chromatography tracks to complete reaction.Cooling, have crystal to separate out, suction filtration, recrystallization can obtain the thiocarbamide-triazole-pyridine compounds with lower formula I structure.
(4) various functional component is added in following ratio: thiocarbamide-triazole-pyridine compounds 40wt%, peregal O-25 1wt%, Virahol 10wt%, potassiumiodide 1wt%, water 48wt%.
By above each component 50 DEG C, under normal pressure, 100r/min constant speed stirs 2 hours, is cooled to normal temperature afterwards, refilters and removes solid impurity, just obtains the supporting corrosion inhibitor product of crude oil decalcifying agent to be prepared.
Reaction formula of the present invention is as follows:
2. the performance evaluation of the supporting inhibiter of crude oil decalcifying agent:
(1) corrosion inhibition evaluation
A. test method
Under industry standard " technical requirements of Q/SH0202-2008 crude oil decalcifying agent " is defined in 30 ± 1 DEG C of test temperatures, in the decalcifying agent solution adding inhibiter, rotary hanging plate corrosion test is carried out with 20# carbon steel lacing film, test piece speed of rotation 75r/min, test period 24h, by the change calculations erosion rate of quality before and after hanging test.Qualified decalcifying agent solution corrosion speed answers≤1mm/a.
B. test-results:
Table 1 rotary hanging plate corrosion test result
| Inhibiter add-on, % | Lacing film erosion rate, mm/a |
| Blank | 13.425 |
| 0.5 | 0.070 |
| 1 | 0.066 |
| 1.5 | 0.064 |
Data as can be seen from table 1, add the corrodibility that inhibiter provided by the invention significantly can control crude oil decalcifying agent solution, for 20# carbon steel lacing film, erosion rate is down to below 0.075mm/a from 13.425mm/a, is much better than the index of erosion rate≤1mm/a that industry standard specifies.
(2) inhibiter is on the impact of crude oil decalcifying agent decalcity:
A. test method:
Industry standard " technical requirements of Q/SH0202-2008 crude oil decalcifying agent " specifies, accurately take a certain amount of crude oil, crude oil decalcifying agent (adding inhibiter provided by the invention), distilled water and emulsion splitter are joined in crude oil in proportion, after abundant mixing, at certain temperature and current field condition, breakdown of emulsion divides water, gets the crude oil sample analysis calcium contents mark after profit layering and calculates decalcification rate.Qualified crude oil decalcifying agent decalcification rate answers >=80%.
B. test-results:
Table 2 crude oil decalcifying test-results
| Inhibiter add-on, % | Crude oil decalcifying rate, % |
| Blank | 85.49 |
| 0.5 | 84.21 |
| 1 | 86.19 |
| 1.5 | 85.33 |
Data as can be seen from table 2, inhibiter provided by the invention is added in crude oil decalcifying agent, crude oil decalcifying rate can reach about 85%, meet decalcification rate that industry standard specifies should >=80% index, therefore inhibiter provided by the invention does not affect the decalcity of decalcifying agent.
Claims (3)
1. the supporting inhibiter of crude oil decalcifying agent, it is characterized in that, by weight percentage, its component and content are: thiocarbamide-triazole-pyridine compounds 30 ~ 50wt%, nonionogenic tenside 0.5 ~ 2wt%, low molecule alcohols 5 ~ 10wt%, inorganic inhibitor 0.5 ~ 2wt%, water 30 ~ 60wt%;
Described thiocarbamide-triazole-pyridine compounds has the structural formula of lower formula I:
Described nonionogenic tenside is paregal O-20, peregal O-25, paregal O-30 or paregal O-35;
Described low molecule alcohols is propiolic alcohol, glycerol, Virahol or ethylene glycol;
Described inorganic inhibitor is potassiumiodide, potassium sulfocyanate, Sodium orthomolybdate or sodium wolframate.
2. the supporting inhibiter of a kind of crude oil decalcifying agent according to claim 1, is characterized in that described nonionogenic tenside is peregal O-25; Described low molecule alcohols is Virahol; Described inorganic inhibitor is potassiumiodide.
3. the preparation method of the supporting inhibiter of a kind of crude oil decalcifying agent according to claim 1, is characterized in that the step of the method is:
(1) take salt of wormwood as catalysts, acetone is reaction solvent, the intermediate generating and there is lower formula II structure is reacted with 3-chloropropionate and methyl benzotriazazole, wherein the mol ratio of salt of wormwood, 3-chloropropionate and methyl benzotriazazole is 1:1:1, temperature of reaction 60 ~ 80 DEG C, 10 ~ 12 hours reaction times;
(2) take ethanol as reaction solvent, the methyl benzotriazazole propionyl hydrazine generating and there is lower formula III structure is reacted with intermediate and hydrazine hydrate, wherein the mol ratio of intermediate and hydrazine hydrate is 1:1, temperature of reaction 60 ~ 80 DEG C, 10 ~ 12 hours reaction times;
(3) take ethyl acetate as reaction solvent, thiocarbamide-triazole-the pyridine compounds with lower formula I structure is generated with potassium sulfocyanate, 2-pyridinecarboxylic chloride and methyl benzotriazazole propionyl hydrazine reaction, wherein the mol ratio of potassium sulfocyanate, 2-pyridinecarboxylic chloride and methyl benzotriazazole propionyl hydrazine is 1:1:0.8, temperature of reaction 60 ~ 80 DEG C, 2 ~ 3 hours reaction times;
(4) by following weight percents, thiocarbamide-triazole-pyridine compounds, nonionogenic tenside, low molecule alcohols, inorganic inhibitor and water are mixed, thiocarbamide-triazole-pyridine compounds 30 ~ 50wt%, nonionogenic tenside 0.5 ~ 2wt%, low molecule alcohols 5 ~ 10wt%, inorganic inhibitor 0.5 ~ 2wt%, water 30 ~ 60wt%; By above each component 30 ~ 50 DEG C, stir 1 ~ 2 hour under normal pressure, stirring velocity 80 ~ 100r/min, is cooled to normal temperature afterwards, by filtering and removing solid impurity, obtains the supporting inhibiter of crude oil decalcifying agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510810108.1A CN105297029B (en) | 2015-11-20 | 2015-11-20 | A kind of supporting corrosion inhibiter of crude oil decalcifying agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510810108.1A CN105297029B (en) | 2015-11-20 | 2015-11-20 | A kind of supporting corrosion inhibiter of crude oil decalcifying agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105297029A true CN105297029A (en) | 2016-02-03 |
| CN105297029B CN105297029B (en) | 2017-10-13 |
Family
ID=55194820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510810108.1A Active CN105297029B (en) | 2015-11-20 | 2015-11-20 | A kind of supporting corrosion inhibiter of crude oil decalcifying agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105297029B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107384472A (en) * | 2016-05-17 | 2017-11-24 | 中国石化扬子石油化工有限公司 | A kind of crude oil metal removal agent |
| CN111925825A (en) * | 2020-07-28 | 2020-11-13 | 广东粤首新科技有限公司 | Scale inhibition and dispersion agent and preparation method and application thereof |
| CN115011967A (en) * | 2022-08-05 | 2022-09-06 | 山东祺裕新材料有限公司 | Low-ammonia-nitrogen acid pickling corrosion inhibitor and use method thereof |
| CN115960609A (en) * | 2022-12-30 | 2023-04-14 | 浙江奥首材料科技有限公司 | Etching solution for etching oxide layer on surface of wafer with high selectivity, preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022554A1 (en) * | 1996-11-18 | 1998-05-28 | Health And Hygiene International Pty. Ltd. | A biocidal corrosion inhibiting composition |
| CN1804125A (en) * | 2006-01-19 | 2006-07-19 | 重庆大学 | Metal pickling inhibitor and method for preparing the same |
| CN101033551A (en) * | 2007-04-16 | 2007-09-12 | 重庆大学 | Acid pickling inhibitor and preparation method thereof |
| CN102226281A (en) * | 2011-06-14 | 2011-10-26 | 北京科技大学 | Non-aldehyde acidification corrosion inhibitor and preparation method thereof |
| CN104651848A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Acidification high temperature corrosion inhibitor and preparation method thereof |
-
2015
- 2015-11-20 CN CN201510810108.1A patent/CN105297029B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022554A1 (en) * | 1996-11-18 | 1998-05-28 | Health And Hygiene International Pty. Ltd. | A biocidal corrosion inhibiting composition |
| CN1804125A (en) * | 2006-01-19 | 2006-07-19 | 重庆大学 | Metal pickling inhibitor and method for preparing the same |
| CN101033551A (en) * | 2007-04-16 | 2007-09-12 | 重庆大学 | Acid pickling inhibitor and preparation method thereof |
| CN102226281A (en) * | 2011-06-14 | 2011-10-26 | 北京科技大学 | Non-aldehyde acidification corrosion inhibitor and preparation method thereof |
| CN104651848A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Acidification high temperature corrosion inhibitor and preparation method thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107384472A (en) * | 2016-05-17 | 2017-11-24 | 中国石化扬子石油化工有限公司 | A kind of crude oil metal removal agent |
| CN107384472B (en) * | 2016-05-17 | 2018-12-11 | 中国石化扬子石油化工有限公司 | A kind of crude oil metal removal agent |
| CN111925825A (en) * | 2020-07-28 | 2020-11-13 | 广东粤首新科技有限公司 | Scale inhibition and dispersion agent and preparation method and application thereof |
| CN115011967A (en) * | 2022-08-05 | 2022-09-06 | 山东祺裕新材料有限公司 | Low-ammonia-nitrogen acid pickling corrosion inhibitor and use method thereof |
| CN115011967B (en) * | 2022-08-05 | 2022-11-04 | 山东祺裕新材料有限公司 | Low-ammonia-nitrogen acid pickling corrosion inhibitor and use method thereof |
| CN115960609A (en) * | 2022-12-30 | 2023-04-14 | 浙江奥首材料科技有限公司 | Etching solution for etching oxide layer on surface of wafer with high selectivity, preparation method and application thereof |
| CN115960609B (en) * | 2022-12-30 | 2023-10-24 | 浙江奥首材料科技有限公司 | Etching solution for etching oxide layer on surface of wafer with high selectivity, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105297029B (en) | 2017-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105297029A (en) | Crude oil decalcifying agent matched corrosion inhibitor and preparation method thereof | |
| CN105755484B (en) | A kind of highly efficiency compositional plant corrosion inhibiter and preparation method and application | |
| CN101928075B (en) | Closed-type circulating cooling water system inhibiter and preparation method thereof | |
| CN108048065A (en) | A kind of oil/gas well corrosion inhibiter and its preparation method and application | |
| Spiccia et al. | Hydrolytic trimer of chromium (III). Synthesis through chromite cleavage and use in the preparation of the" active" trimer hydroxide | |
| CN105483713B (en) | A kind of modified high-molecular compound corrosion inhibitor and preparation method and application | |
| CN101230257A (en) | Method for preparation of lignite resin drilling fluid loss additive | |
| CN105112039B (en) | A kind of high temperature resistant oil-soluble viscosity reducer and preparation method thereof | |
| CN104531101B (en) | Fluid loss additive for boring fluid and preparation method thereof and application | |
| CN102382682B (en) | Hydrogenation scale and corrosion inhibitor and application of scale and corrosion inhibitor | |
| CN106753300B (en) | A kind of double effect compound type hydrate inhibitor and preparation method thereof | |
| CN112280547A (en) | Viscosity-reducing oil displacement agent for super-thick crude oil and preparation method and application thereof | |
| CN106433745A (en) | High-adaptability low-corrosion decalcifying agent of crude oil | |
| CN105238379B (en) | A kind of long-acting corrosion inhibiter of acidification of gas well and its preparation method and application method | |
| CN102181869A (en) | Boiler water-feeding multifunctional corrosion inhibitor and preparation method thereof | |
| CN107059018A (en) | A kind of refinery's corrosion inhibiter and preparation method thereof | |
| RU2601355C1 (en) | Composition for inhibiting formation of hydrates in hydrocarbon-containing raw material | |
| CN106398747B (en) | A kind of high-acid heavy crude oil decalcifying agent and preparation method thereof | |
| CN104562039B (en) | Corrosion inhibitor composition and preparation method thereof | |
| CN111072164B (en) | Composite scale and corrosion inhibitor and application thereof in medium and hard water | |
| CN108977812A (en) | A kind of cold-rolling pickling corrosion inhibiter and preparation method thereof | |
| CN105734580B (en) | A kind of silicon systems macromolecular composite corrosion inhibitor and preparation method thereof | |
| CN104559764A (en) | Novel organosilicone corrosion inhibitor composition and preparation method thereof | |
| CN110484922A (en) | A kind of gas-liquid two-phase carbon dioxide corrosion inhibitor and preparation method thereof | |
| CN112646637A (en) | Turbine oil composition, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Tianjin Chemical Research & Design Institute Applicant before: CNOOC Energy Development Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |