CN105297029B - A kind of supporting corrosion inhibiter of crude oil decalcifying agent and preparation method thereof - Google Patents
A kind of supporting corrosion inhibiter of crude oil decalcifying agent and preparation method thereof Download PDFInfo
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- CN105297029B CN105297029B CN201510810108.1A CN201510810108A CN105297029B CN 105297029 B CN105297029 B CN 105297029B CN 201510810108 A CN201510810108 A CN 201510810108A CN 105297029 B CN105297029 B CN 105297029B
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Abstract
The present invention is a kind of supporting corrosion inhibiter of crude oil decalcifying agent, and its component and content are：Thiocarbamide triazole 30~50wt% of pyridine compounds, 0.5~2wt% of nonionic surfactant, 5~10wt% of low molecule alcohol, 0.5~2wt% of inorganic inhibitor, 30~60wt% of water.The invention further relates to its preparation method, using potassium carbonate as catalyst, acetone is solvent, with 3 chloropropionates and methyl benzotriazazole reaction generation intermediate, then using ethanol as solvent, methyl benzotriazazole propionyl hydrazine is generated with hydration hydrazine reaction, then using ethyl acetate as solvent, thiocarbamide triazole pyridine compounds are generated with potassium rhodanide, 2 pyridinecarboxylic chlorides and methyl benzotriazazole propionyl hydrazine reaction；Finally thiocarbamide triazole pyridine compounds, nonionic surfactant, low molecule alcohol, inorganic inhibitor and water are stirred 1~2 hour at 30~50 DEG C, cools down, filter afterwards, except admittedly miscellaneous rear obtained.The supporting corrosion inhibiter of crude oil decalcifying agent of the present invention can effectively control the corrosivity of crude oil decalcifying agent.
Description
Technical field：
The invention belongs to technical field of metal corrosion protection, it is related to a kind of supporting corrosion inhibiter of crude oil decalcifying agent, the corrosion inhibiter can
Effectively to control corrosion of the crude oil decalcifying agent in desalting in oil refinery process section to hardware and pipeline.
Background technology：
Crude oil decalcifying agent is a kind of Petroleum Refining Additives for being capable of the metal impurities such as efficient removal Calcium in Crude Oil.Crude oil decalcifying agent should
In desalting in oil refinery device, water miscible compound is formed with Calcium in Crude Oil ion in the way of chelating and replace, is made
The metal ions such as calcium ion, with water discharge is cut, reach demetalization purpose from oil phase is transferred to aqueous phase.Filling crude oil decalcifying agent can
Crude oil is removed the metal impurities such as most calcium before atmospheric and vacuum distillation unit is entered, solve because of tenor height in crude oil
Caused refinery's downstream unit fouling, corrosion phenomenon are serious, are hydrocracked, catalyst poisoning is even forever in the process such as catalytic cracking
Long inactivation, and petroleum coke product ash content it is exceeded a series of problems, such as, be that oil refining enterprise adds significant economic benefit.
, can be related to desalting in oil refinery process section during its use but crude oil decalcifying agent is generally highly acid material
Hardware and pipeline cause serious corrosion, influence the operation steady in a long-term of oil plant.
The research in terms of many crude oil decalcifying agents is carried out in recent years both at home and abroad, but has rarely had and match somebody with somebody on crude oil decalcifying agent
Cover the research report of corrosion inhibiter.Therefore, need badly it is a kind of can effectively control the corrosivity of crude oil decalcifying agent, while not influenceing crude oil
The corrosion inhibiter of decalcifying agent performance.
The content of the invention：
In view of the shortcomings of the prior art, the present invention provides one kind using Novel thiourea-triazole-pyridine compounds as main component
The supporting corrosion inhibiter of crude oil decalcifying agent, while providing a kind of method for preparing the supporting corrosion inhibiter of crude oil decalcifying agent.
1. the supporting corrosion inhibiter of crude oil decalcifying agent：
The supporting corrosion inhibiter of a kind of crude oil decalcifying agent that the present invention is provided, it is made up of following component (weight ratio)：
Thiocarbamide-triazole -30~50wt% of pyridine compounds, 0.5~2wt% of nonionic surfactant, low molecule alcohol 5
~10wt%, 0.5~2wt% of inorganic inhibitor, 30~60wt% of water.
Thiocarbamide-triazole-pyridine compounds have the structural formula of following formula (I)：
During nonionic surfactant can be paregal O -20, peregal O-25, paregal O -30 and peregal O-35
A kind of material constitute, be preferred with peregal O-25.
Low molecule alcohol can be that a kind of material is constituted in propilolic alcohol, glycerine, isopropanol, ethylene glycol, using isopropanol as
It is good.
Inorganic inhibitor can be constituted with a kind of material in KI, potassium rhodanide, sodium molybdate, sodium tungstate, using KI as
It is good.
2. the preparation method of the supporting corrosion inhibiter of crude oil decalcifying agent：
Preparation method is divided into four steps：
(1) using potassium carbonate as catalysts, acetone is reaction dissolvent, with 3- chloropropionates and methyl benzotriazazole
Intermediate of the reaction generation with following formula (II) structure, wherein potassium carbonate, 3- chloropropionates and methyl benzotriazazole rubs
You are than being 1:1:1,60~80 DEG C of reaction temperature, 10~12 hours reaction time；
(2) using ethanol as reaction dissolvent, with intermediate and methylbenzene of the hydration hydrazine reaction generation with following formula (III) structure
And triazole propionyl hydrazine, the wherein mol ratio of intermediate and hydrazine hydrate are 1:1,60~80 DEG C of reaction temperature, the reaction time 10~
12 hours；
(3) using ethyl acetate as reaction dissolvent, with potassium rhodanide, 2- pyridinecarboxylic chlorides and methyl benzotriazazole propionyl hydrazine
Thiocarbamide-triazole-pyridine compounds of the reaction generation with following formula (I) structure, wherein potassium rhodanide, 2- pyridinecarboxylic chlorides and methyl
The mol ratio of BTA propionyl hydrazine is 1:1:0.8,60~80 DEG C of reaction temperature, 2~3 hours reaction time；
(4) according to the following percentages by weight by thiocarbamide-triazole-pyridine compounds, nonionic surfactant, low mass molecule alcohol
Class, inorganic inhibitor and water mixing, prepare the supporting corrosion inhibiter of crude oil decalcifying agent, wherein thiocarbamide-triazole-pyridine compounds 30~
50wt%, 0.5~2wt% of nonionic surfactant, 5~10wt% of low molecule alcohol, 0.5~2wt% of inorganic inhibitor, water
30~60wt%；Above each component is stirred 1~2 hour under 30~50 DEG C, normal pressure, 80~100r/min of mixing speed, it
After be cooled to normal temperature, by filtering and removing solid impurity, just obtain product to be prepared.
The supporting corrosion inhibiter corrosion mitigating effect of crude oil decalcifying agent that the present invention is provided is notable, in professional standard《Q/SH0202-2008
Crude oil decalcifying agent technical requirements》When carrying out corrosion test under the conditions of defined, the corrosion rate of crude oil decalcifying agent can be controlled
In below 0.075mm/a, hence it is evident that the technology for being not more than 1mm/a better than crude oil decalcifying agent corrosion rate as defined in professional standard refers to
Mark.Meanwhile, add after the supporting corrosion inhibiter of crude oil decalcifying agent that provides of the present invention, the decalcity of crude oil decalcifying agent not by
To detrimental effect, decalcification rate stabilization meets the requirement of professional standard more than 80%.
Embodiment：
1. the preparation of the supporting corrosion inhibiter of crude oil decalcifying agent：
(1) added in equipped with agitator, the 250mL four-hole boiling flasks of reflux condensing tube 0.15mol methyl benzotriazazoles,
0.15mol chloropropionates, 160mL reaction dissolvents acetone and 0.15mol catalysts potassium carbonate, are heated back at 80 DEG C
Stream, after reacting 12 hours, to product suction filtration, filtrate decompression distillation obtains the intermediate with following formula (II) structure.
(2) 0.15mol hydrazine hydrates, 0.15mol are added in equipped with agitator, the 250mL four-hole boiling flasks of reflux condensing tube
Intermediate (II) and 100mL ethanol, after heating stirring flow back 12 hours at 80 DEG C, reaction solution are distilled, steamed about
60mL liquid, Liquid Residue, which is cooled to room temperature, solid precipitation, and suction filtration is washed with ethanol.Drying, weighs.Obtain with following formula
(III) the white methyl benzotriazazole propionyl hydrazine solid of structure.
(3) under drying condition, the acetic acid second of potassium rhodanide containing 0.015mol (drying) is added in 250mL four-hole boiling flasks
Ester solution, is slowly added dropwise 0.015mol2- pyridinecarboxylic chlorides at 60 DEG C thereto while stirring, continues stirring reaction 2h after adding,
Filtering, removes the potassium chloride of generation.0.012mol methyl benzotriazazole propionyl hydrazine solids (III), back flow reaction are added in filtrate
4h, thin-layer chromatography tracks to complete reaction.Cooling, there is crystal precipitation, and suction filtration, recrystallization can be obtained with following formula (I) structure
Thiocarbamide-triazole-pyridine compounds.
(4) various functions component is added in following ratio：Thiocarbamide-triazole-pyridine compounds 40wt%, paregal O-
251wt%, isopropanol 10wt%, KI 1wt%, water 48wt%.
By above each component under 50 DEG C, normal pressure, 100r/min constant speed is stirred 2 hours, and normal temperature is cooled to afterwards, is refiltered
Solid impurity is removed, the supporting corrosion inhibitor product of crude oil decalcifying agent to be prepared is just obtained.
The reaction equation of the present invention is as follows：
2. the performance evaluation of the supporting corrosion inhibiter of crude oil decalcifying agent：
(1) corrosion inhibition evaluation
A. test method
Professional standard《Q/SH 0202-2008 crude oil decalcifying agent technical requirements》Regulation is used under 30 ± 1 DEG C of test temperatures
20# carbon steels lacing film carries out rotary hanging plate corrosion test, test piece rotary speed 75r/ in the decalcification agent solution for add corrosion inhibiter
Min, test period 24h, corrosion rate is calculated by the change of quality before and after hanging test.Qualified decalcifying agent solution corrosion speed
Rate answers≤1mm/a.
B. result of the test：
The rotary hanging plate corrosion test result of table 1
| Corrosion inhibiter addition, % | Lacing film corrosion rate, mm/a |
| Blank | 13.425 |
| 0.5 | 0.070 |
| 1 | 0.066 |
| 1.5 | 0.064 |
It can be seen from the data in Table 1 that crude oil decalcifying agent solution can significantly be controlled by adding the corrosion inhibiter of the invention provided
Corrosivity, for 20# carbon steel lacing films, corrosion rate is down to below 0.075mm/a from 13.425mm/a, is much better than industry mark
Corrosion rate≤1mm/a index as defined in accurate.
(2) influence of the corrosion inhibiter to crude oil decalcifying agent decalcity：
A. test method：
Professional standard《Q/SH 0202-2008 crude oil decalcifying agent technical requirements》Regulation, accurately weighs a certain amount of crude oil,
Crude oil decalcifying agent (adding the corrosion inhibiter that the present invention is provided), distilled water and demulsifier are proportionally added into crude oil, it is fully mixed
After conjunction, the demulsification point water at certain temperature and current field condition takes the crude oil sample analysis calcium content fraction after profit layering and calculated
Decalcification rate.Qualified crude oil decalcifying agent decalcification rate answers >=80%.
B. result of the test：
The crude oil decalcifying result of the test of table 2
| Corrosion inhibiter addition, % | Crude oil decalcifying rate, % |
| Blank | 85.49 |
| 0.5 | 84.21 |
| 1 | 86.19 |
| 1.5 | 85.33 |
It can be seen from the data in Table 2 that adding the corrosion inhibiter that the present invention is provided, crude oil decalcifying rate energy in crude oil decalcifying agent
85% or so is enough reached, the index that decalcification rate as defined in professional standard answers >=80%, therefore the corrosion inhibiter that the present invention is provided is met
Have no effect on the decalcity of decalcifying agent.
Claims (3)
1. a kind of supporting corrosion inhibiter of crude oil decalcifying agent, it is characterised in that by weight percentage, its component and content are：Thiocarbamide-three
Azoles -30~50wt% of pyridine compounds, 0.5~2wt% of nonionic surfactant, low molecule alcohol 5~10wt% are inorganic slow
Lose 0.5~2wt% of agent, 30~60wt% of water；And the constituent content sum of each component is absolutely；
Thiocarbamide-triazole-the pyridine compounds have the structural formula of following formula (I)：
The nonionic surfactant is paregal O -20, peregal O-25, paregal O -30 or paregal O -35；
The low molecule alcohol is propilolic alcohol, glycerine, isopropanol or ethylene glycol；
The inorganic inhibitor is KI, potassium rhodanide, sodium molybdate or sodium tungstate.
2. the supporting corrosion inhibiter of a kind of crude oil decalcifying agent according to claim 1, it is characterised in that the non-ionic surface is lived
Property agent is peregal O-25；The low molecule alcohol is isopropanol；The inorganic inhibitor is KI.
3. a kind of preparation method of the supporting corrosion inhibiter of crude oil decalcifying agent described in claim 1, it is characterised in that the step of this method
Suddenly it is：
(1) using potassium carbonate as catalysts, acetone is reaction dissolvent, is reacted with 3- chloropropionates and methyl benzotriazazole
The mol ratio of intermediate, wherein potassium carbonate, 3- chloropropionate and methyl benzotriazazole of the generation with following formula (II) structure
For 1:1:1,60~80 DEG C of reaction temperature, 10~12 hours reaction time；
(2) using ethanol as reaction dissolvent, with intermediate and methyl benzo three of the hydration hydrazine reaction generation with following formula (III) structure
Nitrogen azoles propionyl hydrazine, the wherein mol ratio of intermediate and hydrazine hydrate are 1:1,60~80 DEG C of reaction temperature, the reaction time 10~12 is small
When；
(3) using ethyl acetate as reaction dissolvent, with potassium rhodanide, 2- pyridinecarboxylic chlorides and methyl benzotriazazole propionyl hydrazine reaction
Thiocarbamide-triazole-pyridine compounds of the generation with following formula (I) structure, wherein potassium rhodanide, 2- pyridinecarboxylic chlorides and methyl benzo
The mol ratio of triazole propionyl hydrazine is 1:1:0.8,60~80 DEG C of reaction temperature, 2~3 hours reaction time；
(4) according to the following percentages by weight by thiocarbamide-triazole-pyridine compounds, nonionic surfactant, low molecule alcohol, nothing
Machine corrosion inhibiter and water mixing, thiocarbamide-triazole -30~50wt% of pyridine compounds, nonionic surfactant 0.5~2wt% are low
Molecule 5~10wt% of alcohols, 0.5~2wt% of inorganic inhibitor, 30~60wt% of water, and the constituent content sum of each component is
Absolutely；Above each component is stirred 1~2 hour under 30~50 DEG C, normal pressure, 80~100r/min of mixing speed, afterwards
Normal temperature is cooled to, by filtering and removing solid impurity, the supporting corrosion inhibiter of crude oil decalcifying agent is obtained.
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| 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 |
| CN111925825B (en) * | 2020-07-28 | 2022-10-04 | 广东粤首新科技有限公司 | Scale inhibition and dispersion agent and preparation method and application 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 |
| 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 |
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| 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 |
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| 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 |
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