CN106337188A - Preparation and application of phosphate-free type high temperature inhibitor - Google Patents
Preparation and application of phosphate-free type high temperature inhibitor Download PDFInfo
- Publication number
- CN106337188A CN106337188A CN201610868701.6A CN201610868701A CN106337188A CN 106337188 A CN106337188 A CN 106337188A CN 201610868701 A CN201610868701 A CN 201610868701A CN 106337188 A CN106337188 A CN 106337188A
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- fatty acid
- high temperature
- temperature
- preparation
- phosphate
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/145—Amides; N-substituted amides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to preparation and application of a phosphate-free type high temperature inhibitor. The preparation comprises the steps that fatty acid and a solvent with the molar ratio being 1:(2-4) are heated to 80-120 DEG C and are continuously stirred, and diamine is dropwise added with the dropwise-adding time being controlled within 1-3h; after dropwise-adding is completed, the temperature is increased to 150-180 DEG C, stirring is continued for 3-6h, and dehydration is conducted to enable the reaction to be complete; and fatty acid aminoacid amide is synthesized, 30-50% of the fatty acid aminoacid amide, 20-30% of isobutene sulfide (T321) and 30-50% of heavy aromatic solvent oil are blended by mass, and the fatty acid aminoacid amide high temperature inhibitor is prepared through compounding. The phosphate-free type high temperature inhibitor can be used for equipment and pipelines corroded by high temperature in the oil refining process, in the initial stage, the filling quantity is 100-200ppm, and after stabilization, the filling quantity is 10-20ppm; and the phosphate-free type high temperature inhibitor is stable in product performance, and has the advantages of being free of phosphate, environmentally friendly, high in oxidation resistance, suitable for automatic dosing control, convenient to use and the like.
Description
Technical field
The invention belongs to Application in Chemical Engineering field, particularly to a kind of preparation of no phosphorous high-temperature corrosion inhibitor and application.
Background technology
The corrosion of oil plant hardware can be divided into cold end corrosion and high temperature corrosion, and wherein high temperature corrosion is to occur
More than 250 DEG C of high-temperature part, based on chemical attack, refining equipment corrodes aggravation with fluid during heating up；
In recent years, the import of the continuous Deep mining with oil field and a large amount of high-acid crude oil, crude oil in China increasingly heaviness, in poor quality,
Its acid number is made to improve constantly also increasingly severe to the corrosion of crude oil processing equipment, distinct issues are exactly by aphthenic acids and sulphur
The etching problem that the corrosive medium of compound class causes, Atmospheric vacuum steams the Corrosion behavior wherein being caused by aphthenic acids most serious of all
High temperature position in distillation unit;High temperature corrosion is the high-temperature part occurring more than 250 DEG C, and based on chemical attack, oil refining sets
Standby corrode aggravation with fluid during heating up；Also contain substantial amounts of aphthenic acids, it is gold in the component of crude oil simultaneously
Belong to the topmost problem of equipment corrosion and so far the structure of aphthenic acids is had been carried out with many researchs, research shows, aphthenic acids is
A kind of organic acid containing saturated cyclic structure being present in oil, its formula is cnhn+zo2, and (wherein n is carbon atom
Number, z is 0 or negative integer)；Aphthenic acids, as a class organic acid, has the chemical property of common carboxylic acid, and its acidity compares phenol
Class is high, but lower than carboxylic acid, and just because aphthenic acids is acidic materials, aphthenic acids can cause to hardware to corrode, particularly
Low molecule aphthenic acids acidity is also stronger, equipment is caused corrode even more serious, especially in larger acid number and higher temperature
Under acting under degree, equipment corrosion is more severe simultaneously.
For suppressing the corrosiveness of aphthenic acids, it is anti-corrosion to carry out that oil plant takes very many measures, alleviates aphthenic acids
Corrode and mainly have following several method:
1. physical method, including to Processes and apparatus structural adjustment and updating apparatus material
The process route of Reasonable adjustment oil refining can reduce the corrosion of medium local, avoid localized concentrations on device structure as far as possible
Enrichment, flow velocity is too high, localized hyperthermia, fluid directly wash away, and can reduce the corrosion to hardware for the aphthenic acids with this；Also may be used
To control oil acid corrosion by selecting suitable material come updating apparatus.Modern petroleum refining industry is faced with corrosivity increasingly
Strong production environment, and the corrosion resistance that the various corrosion resistant alloy materials using can not meet different levels requires " new type corrosion resistant
The application of austenitic alloy and two phase stainless steel has obvious development.Fully scalable material costly, should in actual production
With in usually adopt process for modifying surface, change surface characteristics of metal, to improve the antiseptic property of metal material.
2. chemical method, is in harmonious proportion, removes aphthenic acids and use corrosion inhibiter including crude oil.
Hardware can be produced when acid number is more than 0.5mgkoh/g in crude oil medium and significantly corrode, therefore permissible
Selectively crude oil low to crude oil high for acid number and acid number is mixed, make the total acid number of crude oil be less than 0.5mgkoh/g,
When crude oil refinery starts, just can effectively reduce Crude Oil Naphthenic Acid Corrosion.Because this method does not need extra charge and throwing
Money judges it is only necessary to make favourable analysis in decision-making and plan, using than wide.And remove aphthenic acids, be directly from
Aphthenic acids is removed in crude oil.The method that acid-containing raw oil removes aphthenic acids mainly has: alkali neutralisation, adsorbing separation, hydrogenation and removing, takes out
Carry and separate, be heat-treated depickling, alkaline metal oxide depickling etc..
These methods respectively have its pluses and minuses, all do not have real industrialization.At present, the most frequently used, maximally effective in oil plant
Method be exactly carried out using corrosion inhibiter anti-corrosion to protect hardware.The kind of high-temperature corrosion inhibitor is a lot, the high temperature inhibition of phosphorus system
The corrosion mitigating effect of agent is relatively good, but can cause following process catalyst poisoning and environmental issue, and using being restricted, non-phosphorus system delays
Erosion agent corrosion mitigating effect is poor, has no the report of commercial Application.
Content of the invention
Inventing technical problem to be solved is for above-mentioned state of the art, present invention aim at providing one kind
Corrosion mitigating effect is good and is suitable for industrial without phosphorus high-temperature corrosion inhibitor.
For solving above technical problem, a kind of technical scheme that the present invention takes is:
A kind of preparation of no phosphorous high-temperature corrosion inhibitor, key step is as follows:
(1) add aliphatic acid and solvent in four-hole boiling flask, be heated to 80～120 DEG C, be stirred continuously and drip diamines, described
Aliphatic acid is 1:2～4 with the mol ratio of described diamines, and time for adding controls in 1～3h；After being added dropwise to complete, by temperature liter
To 150-180 DEG C, continue stirring 3～6 h, be dehydrated to reaction completely；Finally steam the solvent in reaction；
(2) fatty acid amino amide synthesizing in step (1), according to mass ratio: fatty acid amino amide 30～50%, sulfuration
Isobutene (t321) 20～30%, heavy aromatic solvent oil 30～50% is allocated, and makes fatty acid amino amide high temperature inhibition
Agent.
Preferably, described aliphatic acid is oleic acid, laurate or stearic acid.
Preferably, described solvent is toluene or dimethylbenzene.
Preferably, described diamines is cyclohexanediamine or methyl ring pentanediamine.
What the present invention solved that its technical problem adopted another solution is that
A kind of application of no phosphorous high-temperature corrosion inhibitor, this corrosion inhibiter is used for equipment and the pipeline of oil refining process high temperature corrosion, makes
It is 100～200ppm with initial stage adding amount, the adding amount after stablizing is 10～20ppm.
The positive effect of the present invention shows: the inhibition product of the present invention meets the requirement that in industry, corrosion inhibition rate is more than 85%, should
Compound product, in the case that addition is suitable with containing phosphor corrosion inhibitor, greatly improves corrosion mitigating effect；And properties of product are stable, tool
Have the advantages that without phosphorus, environmental protection, non-oxidizability strong it is adaptable to Automatic Dosing control easy to use.
Specific embodiment
Below embodiments of the invention are elaborated, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following enforcements
Example.
Embodiment 1: add 282g oleic acid and 40g dimethylbenzene in four-hole boiling flask, be heated to 80～100 DEG C, be stirred continuously
And drip 230g cyclohexanediamine, it is added dropwise to complete in 2h；After being added dropwise to complete, temperature is risen to 150～180 DEG C, continue stirring 3～
6 h, are dehydrated to reaction completely；Finally steam the solvent in reaction.
According to fatty acid amino amide 30%, sulfide isobutene (t321) 20%, the ratio of heavy aromatic solvent oil 50% is carried out
Allotment, makes fatty acid amino amide high-temperature corrosion inhibitor.
Embodiment 2: add 284g stearic acid and 30g toluene in four-hole boiling flask, be heated to 100～120 DEG C, constantly stir
Mix and drip 345g cyclohexanediamine, be added dropwise to complete in 3h；After being added dropwise to complete, temperature is risen to 180～200 DEG C, continue stirring 3
～6 h, are dehydrated to reaction completely；Finally steam the solvent in reaction.
According to fatty acid amino amide 35%, sulfide isobutene (t321) 25%, the ratio of heavy aromatic solvent oil 40% is carried out
Allotment, makes fatty acid amino amide high-temperature corrosion inhibitor.
Embodiment 3: add 200g laurate and 40g dimethylbenzene in four-hole boiling flask, be heated to 80～100 DEG C, constantly stir
Mix and drip 230g methyl ring pentanediamine, be added dropwise to complete in 2h；After being added dropwise to complete, temperature is risen to 160～180 DEG C, continue
Stirring 3～5 h, are dehydrated to reaction completely；Finally steam the solvent in reaction.
According to fatty acid amino amide 30%, sulfide isobutene (t321) 25%, the ratio of heavy aromatic solvent oil 45% is carried out
Allotment, makes fatty acid amino amide high-temperature corrosion inhibitor.
Embodiment 4: add the acid of 282g oleic acid and 30g toluene in four-hole boiling flask, be heated to 100～120 DEG C, constantly stir
Mix and drip 345g methyl ring pentanediamine, be added dropwise to complete in 3h；After being added dropwise to complete, temperature is risen to 180～200 DEG C, continue
Stirring 4～6 h, are dehydrated to reaction completely；Finally steam the solvent in reaction.
According to fatty acid amino amide 35%, sulfide isobutene (321) 30%, the ratio of heavy aromatic solvent oil 35% is adjusted
Join, make fatty acid amino amide high-temperature corrosion inhibitor.
Corrosion inhibiter evaluation experimental example: using high temperature and high pressure kettle simulated field environment, synthesis corrosion inhibiter product is carried out
Lab-evaluation, used by test, corrosive medium solution is formulated by rendering industry white oil and aphthenic acids, the final acid preparing liquid
It is worth for 12mgkoh/g, sample material is 20# carbon steel, and it is processed to the bar shaped test piece of 30mm × 10mm × 5mm., test temperature
Degree selects 270 DEG C -320 DEG C of aphthenic acids heavy corrosion sensitizing range.Concrete operation method is as follows:
In 1000ml dynamic high temperature autoclave, aphthenic acids/white oil solution containing a certain amount of corrosion inhibiter for the injection, 2 are polished
The band sample weighed is contained on fixture to be put in kettle, checks the air-tightness of autoclave, closes and hold one's breath after carrying out letting nitrogen in and deoxidizing 2h
Source, opens stirring, is warming up to 270 DEG C～320 DEG C about and carries out constant temperature test 6h, takes out sample when temperature is down to room temperature,
Sample after test is put removing surface and oil contaminant in people's petroleum ether, polishes off surface inhibitor film with rubber, then use acetone
Wiped clean, dries and weighs, and calculates corrosion rate and corrosion inhibition rate.
Embodiment 1～4 corrosion inhibition evaluation result:
After the completion of evaluation, surface of test piece has adsorbed one layer of fine and close diaphragm, smooth surface, no local corrosion.By above-mentioned data
As can be seen that the corrosion inhibiter of the present invention has reached more than 90% to the inhibition efficiency of 20# steel.
By substantial amounts of experiment and corrosion inhibition rate evaluation it has been found that by fatty acid amino amide class compound and organic many sulphur
It is best that ether compound carries out a certain proportion of compounding corrosion mitigating effect；Therefore we have screened multiple fatty acid amino amide class chemical combination
Thing and organic polythiaether compound, carry out orthogonal experiment, choose two of which and are compounded；This compound product addition with contain
In the case that phosphor corrosion inhibitor is suitable, greatly improve corrosion mitigating effect.
Claims (5)
1. a kind of preparation method of no phosphorous high-temperature corrosion inhibitor is it is characterised in that key step is as follows:
(1) add aliphatic acid and solvent in four-hole boiling flask, be heated to 80～120 DEG C, be stirred continuously and drip diamines, described
Aliphatic acid is 1:2～4 with the mol ratio of described diamines, and time for adding controls in 1～3h；After being added dropwise to complete, by temperature liter
To 150-180 DEG C, continue stirring 3～6 h, be dehydrated to reaction completely；Finally steam the solvent in reaction；
(2) fatty acid amino amide synthesizing in step (1), according to mass ratio: fatty acid amino amide 30～50%, sulfuration
Isobutene (t321) 20～30%, heavy aromatic solvent oil 30～50% is allocated, and makes fatty acid amino amide high temperature inhibition
Agent.
2. a kind of preparation method of no phosphorous high-temperature corrosion inhibitor according to claim 1 is it is characterised in that described aliphatic acid
For oleic acid, laurate or stearic acid.
3. a kind of preparation method of no phosphorous high-temperature corrosion inhibitor according to claim 1 is it is characterised in that described solvent is
Toluene or dimethylbenzene.
4. a kind of preparation method of no phosphorous high-temperature corrosion inhibitor according to claim 1 is it is characterised in that described diamines is
Cyclohexanediamine or methyl ring pentanediamine.
5. a kind of application of no phosphorous high-temperature corrosion inhibitor is it is characterised in that this corrosion inhibiter is used for the corrosion of oil refining process high temperature
Equipment and pipeline, are 100～200ppm using initial stage adding amount, the adding amount after stablizing is 10～20ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610868701.6A CN106337188A (en) | 2016-09-30 | 2016-09-30 | Preparation and application of phosphate-free type high temperature inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610868701.6A CN106337188A (en) | 2016-09-30 | 2016-09-30 | Preparation and application of phosphate-free type high temperature inhibitor |
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| Publication Number | Publication Date |
|---|---|
| CN106337188A true CN106337188A (en) | 2017-01-18 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610868701.6A Pending CN106337188A (en) | 2016-09-30 | 2016-09-30 | Preparation and application of phosphate-free type high temperature inhibitor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107675187A (en) * | 2017-07-21 | 2018-02-09 | 中海油天津化工研究设计院有限公司 | A kind of non-phosphorus system's high-temperature corrosion inhibitor and preparation method thereof |
| CN115233225A (en) * | 2022-07-25 | 2022-10-25 | 威海翔宇环保科技股份有限公司 | Amphoteric environment-friendly high-temperature corrosion inhibitor and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130702A (en) * | 2006-08-23 | 2008-02-27 | 中国石油天然气股份有限公司 | Corrosion inhibitor for desalting and dewatering device of refinery and preparation and use methods thereof |
-
2016
- 2016-09-30 CN CN201610868701.6A patent/CN106337188A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130702A (en) * | 2006-08-23 | 2008-02-27 | 中国石油天然气股份有限公司 | Corrosion inhibitor for desalting and dewatering device of refinery and preparation and use methods thereof |
Non-Patent Citations (1)
| Title |
|---|
| 徐兵等: "脂肪酸氨基酰胺高温缓蚀剂的研究", 《镇江高专学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107675187A (en) * | 2017-07-21 | 2018-02-09 | 中海油天津化工研究设计院有限公司 | A kind of non-phosphorus system's high-temperature corrosion inhibitor and preparation method thereof |
| CN115233225A (en) * | 2022-07-25 | 2022-10-25 | 威海翔宇环保科技股份有限公司 | Amphoteric environment-friendly high-temperature corrosion inhibitor and preparation method thereof |
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Application publication date: 20170118 |
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