CN107338072B - Reformer corrosion inhibiter and preparation method thereof - Google Patents
Reformer corrosion inhibiter and preparation method thereof Download PDFInfo
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- CN107338072B CN107338072B CN201710616053.XA CN201710616053A CN107338072B CN 107338072 B CN107338072 B CN 107338072B CN 201710616053 A CN201710616053 A CN 201710616053A CN 107338072 B CN107338072 B CN 107338072B
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- reformer
- corrosion inhibiter
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to reformer corrosion inhibiter and preparation method thereof.Reformer corrosion inhibiter of the invention includes amine complexing agent, and the amine complexing agent is made of 40~55 weight % of monoethanolamine, 30~45 weight % of diethanol amine and 10~20 weight % of triethanolamine.The invention has the benefit that the present invention is oil-soluble film-forming type substance; it can be adsorbed on reformer apparatus surface with polarity gene, form one layer of unimolecule water-resistance protective film, there is strong repulsive interaction to hydrogen ion; prevent hydrogen ion to the close of metal equipment, to slow down HCl and H2The effect of S.
Description
Technical field
The invention belongs to corrosion inhibiter fields, and in particular to a kind of reformer corrosion inhibiter and preparation method thereof.
Background technique
Currently, crude quality is declining, the content of the asphalt colloid in crude oil is constantly increased, the corrosion feelings of oil refinery equipment
Condition is also increasingly severe.Existing reformer corrosion inhibiter is mostly quaternary ammonium salt, organic polymer, this seed type corrosion inhibiter is in inhibition
Ineffective, by it in the case where gum level height, corrosion mitigating effect is poor, and such corrosion inhibiter certain journey in use
It will affect the activity of catalyst on degree, to influence enterprises production efficiency, improve enterprise's production cost.
Summary of the invention
Of the existing technology in order to solve the problems, such as, the present invention provides a kind of reformer corrosion inhibiter and its preparation sides
Method, it is excellent with anti-corrosion effect, nontoxic have no irritating odor, have no adverse effects etc. to device oil quality and downstream unit spies
Point.
The object of the present invention is to provide a kind of reformer corrosion inhibiter
The reformer corrosion inhibiter of specific embodiment according to the present invention, the corrosion inhibiter includes amine complexing agent, described
Amine complexing agent is by 40~55 weight % of monoethanolamine, 30~45 weight % of diethanol amine and 10~20 weight % group of triethanolamine
At.
The reformer corrosion inhibiter of specific embodiment according to the present invention, the corrosion inhibiter further includes synergist, described
The weight proportion of synergist and the amine complexing agent is 1:1~2.
The reformer corrosion inhibiter of specific embodiment, the synergist include glycerine and lemon according to the present invention
The weight proportion of acid, glycerine and citric acid is 1:1~3.
The weight proportion of the reformer corrosion inhibiter of specific embodiment according to the present invention, glycerine and citric acid is 1:
1。
It is a further object to provide a kind of preparation methods of reformer corrosion inhibiter.
The preparation method of the reformer corrosion inhibiter of specific embodiment party according to the present invention, comprising the following steps: take ring
The ratio between amount of substance of oxidative ethane and ammonia, ethylene oxide and ammonia is 1:4~5, reacts under the conditions of temperature-pressure, it is compound to obtain amine
Agent.
The preparation method of the reformer corrosion inhibiter of specific embodiment party according to the present invention, before reaction, dissolves ammonia in
In water, the concentration of ammonia in water is 50~70%.
The preparation method of the reformer corrosion inhibiter of specific embodiment party according to the present invention, ethylene oxide and ammonia reaction
When, the pressure that reaction is arranged is 15~20MPa, and keeping the temperature of reaction is 130~180 DEG C, is reacted 2 hours.
The preparation method of the reformer corrosion inhibiter of specific embodiment party according to the present invention, ethylene oxide and ammonia reaction
When, the pressure that reaction is arranged is 16MPa, and keeping the temperature of reaction is 150 DEG C, is reacted 2 hours.
The preparation method of the reformer corrosion inhibiter of specific embodiment party, ammonia are complete with reacting ethylene oxide according to the present invention
Synergist is added into resulting amine complexing agent by Cheng Hou, and the synergist of addition and the mass ratio of amine complexing agent are 1:1~2.
The preparation method of the reformer corrosion inhibiter of specific embodiment party according to the present invention, the synergist of addition include third
The weight proportion of triol and citric acid, glycerine and citric acid is 1:1~3.
The invention has the benefit that
The present invention is oil-soluble film-forming type substance, can be adsorbed on reformer apparatus surface with polarity gene, forms one layer
Unimolecule water-resistance protective film, this layer of protective film and hydrogen ion effect generate positively charged ion, reaction equation RNH2++H+→
RNH3+。
Since the hydrogen ion (HCl and HS dissociation after the hydrogen ion that is formed) in this ion pair solution has strong repulsion to make
With prevention hydrogen ion is to the close of metal equipment, to slow down HCl and H2The effect of S, amine complexing agent of the present invention is in H2S-
HCl-H2There is good corrosion mitigating effect in O-shaped corrosiveness.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
Embodiment 1
Reformer corrosion inhibiter of the invention includes amine complexing agent, the amine complexing agent by 40 weight % of monoethanolamine,
40 weight % of diethanol amine and 20 weight % of triethanolamine composition.
The preparation method of reformer corrosion inhibiter of the invention, comprising the following steps:
Ethylene oxide and ammonia are taken, the ratio between ethylene oxide and the amount of substance of ammonia are 1:4, and reaction need to carry out under elevated pressure, are grasped
Make pressure in 15Mpa, temperature is 130 DEG C, 2 hours reacted, room temperature is then gradually cooling to, obtain product amine complexing agent,
Middle monoethanolamine, diethanol amine and triethanolamine are respectively 40%, 40% and 20%.
Embodiment 2
Reformer corrosion inhibiter of the invention includes amine complexing agent, the amine complexing agent by 50 weight % of monoethanolamine,
35 weight % of diethanol amine and 15 weight % of triethanolamine composition.
The preparation method of reformer corrosion inhibiter of the invention, comprising the following steps: take ethylene oxide and ammonia, ammonia is dissolved in
In water, for the control of concentration in water 50%, the ratio between ethylene oxide and the amount of substance of ammonia are 1:5, reaction need under elevated pressure into
Row, for usual operating pressure in 16Mpa, temperature is 150 DEG C, reacts 2 hours, is then gradually cooling to room temperature, it is compound to obtain amine
Agent, wherein monoethanolamine 30%, diethanol amine 35%, triethanolamine 15%.
Embodiment 3
Reformer corrosion inhibiter of the invention includes amine complexing agent and synergist, the weight of synergist and the amine complexing agent
Amount proportion is 1:1；
The amine complexing agent is by 40 weight % of monoethanolamine, 45 weight % of diethanol amine and 15 weight % group of triethanolamine
At；
Synergist includes glycerine and citric acid, and the weight proportion of glycerine and citric acid is 1:1.
The preparation method of reformer corrosion inhibiter of the invention, comprising the following steps:
(1) ethylene oxide and ammonia are taken, the ratio between ethylene oxide and the amount of substance of ammonia are 1:4~5, and reaction needs under elevated pressure
It carries out, for usual operating pressure in 15Mpa, temperature is 150 DEG C, reacts 2 hours, is then gradually cooling to room temperature, and it is multiple to obtain amine
Mixture, wherein monoethanolamine is 40%, diethanol amine 45%, triethanolamine 15% for measurement；
(2) it is added the synergist of equal quality into reaction solution, synergist is that mass concentration is 50% to mix with 1:1
Glycerine and citric acid are kept stirring one hour.
Embodiment 4
Reformer corrosion inhibiter of the invention includes amine complexing agent and synergist, the weight of synergist and the amine complexing agent
Amount proportion is 1:1.5；
The amine complexing agent is by 50 weight % of monoethanolamine, 40 weight % of diethanol amine and 10 weight % group of triethanolamine
At；
Synergist includes glycerine and citric acid, and the weight proportion of glycerine and citric acid is 1:2.
The preparation method of reformer corrosion inhibiter of the invention, comprising the following steps:
(1) take ethylene oxide and ammonia, the ratio between amount of substance of ethylene oxide and ammonia is 1:4.5, reaction need under elevated pressure into
Row, for usual operating pressure in 16Mpa, temperature is 170 DEG C, reacts 2 hours, is then gradually cooling to room temperature, obtaining product is
Amine complexing agent, wherein monoethanolamine 50%, diethanol amine 40% and triethanolamine 10%；
(2) it is added the synergist of equal quality into reaction solution, synergist is that mass concentration is 50% to mix with 1:2
Glycerine and citric acid are kept stirring one hour.
Embodiment 5
Reformer corrosion inhibiter of the invention includes amine complexing agent and synergist, the weight of synergist and the amine complexing agent
Amount proportion is 1:2；
The amine complexing agent is by 55 weight % of monoethanolamine, 30 weight % of diethanol amine and 15 weight % group of triethanolamine
At；
Synergist includes glycerine and citric acid, and the weight proportion of glycerine and citric acid is 1:3.
The preparation method of reformer corrosion inhibiter of the invention, comprising the following steps:
(1) ethylene oxide and ammonia are taken, the ratio between ethylene oxide and the amount of substance of ammonia are 1:5, and ammonia is dissolved in water, and ammonium hydroxide is dense
Degree control is 60%, and for operation pressure in 18Mpa, temperature is 160 DEG C, reacts 2 hours, is then gradually cooling to room temperature,
Obtaining product is amine complexing agent, and wherein the quantum of output of monoethanolamine, diethanol amine and triethanolamine is respectively 55%, 30% and
15%；
(2) it is added the synergist of equal quality into reaction solution, synergist is that mass concentration is 50% to mix with 1:1
Glycerine and citric acid are kept stirring one hour.
Embodiment 6
Reformer corrosion inhibiter of the invention includes amine complexing agent and synergist, the weight of synergist and the amine complexing agent
Amount proportion is 1:1；
The amine complexing agent is by 49 weight % of monoethanolamine, 38 weight % of diethanol amine and 13 weight % group of triethanolamine
At；
Synergist includes glycerine and citric acid, and the weight proportion of glycerine and citric acid is 1:1.
The preparation method of reformer corrosion inhibiter of the invention, comprising the following steps:
(1) ethylene oxide and ammonia are taken, the ratio between ethylene oxide and the amount of substance of ammonia are 1:4, and ammonia is dissolved in water, concentration control
System is 70%；In 16Mpa, temperature remains 150 DEG C, reacts 2 hours for operating pressure control in reaction process；Then gradually cold
But to room temperature, obtain product amine complexing agent, wherein the quantum of output of monoethanolamine, diethanol amine and triethanolamine be respectively 49%,
38% and 13%,；
(2) it is added the synergist of equal quality into reaction solution, synergist is that mass concentration is 50% to mix with 1:1
Glycerine and citric acid are kept stirring one hour.
Corrosion inhibiter of the invention is mainly used for the anti-corrosion of oil plant reformer, according to the oil product of processing and produced on-site
Technique requirement, corrosion inhibiter plus dosage generally between 10~30PPM, when of the invention plus dosage is 20ppm, indoor dynamic
Corrosion inhibition rate reaches 90% or more, can effectively alleviate the corrosion condition of equipment, ensure that the continuous operation of device.
Have compared with traditional quaternary ammonium salt corrosion inhibiter plus dosage is small, the more excellent feature of corrosion mitigating effect ensure that dress
While setting continuous safe operation, the production cost of enterprise is reduced, is effectively controlled the etching problem of reformer.
The present invention measures data, the variation of elbow wall thickness and the change of device and feed impurities in the water of injection front and back respectively
Change, concrete outcome see the table below.
Water number is according to analysis before and after 1 use of table
Conclusion: after injecting corrosion inhibiter of the invention, Fe in reformer2+Concentration substantially reduces, and is dropped to by 135mg/L or so
1mg/L or less；PH value rises in water after injection, becomes alkalescent by faintly acid, this shows the inhibition of corrosion inhibiter of the invention
Effect is obvious.
Comparative example use quaternary ammonium salt product in the prior art, corrosion inhibiter of the invention in contrast, Fe2+Concentration is lower
And stablize after use, pH is relatively stable.
The variation of elbow wall thickness before and after 2 corrosion inhibiter use of table
Conclusion: after injecting corrosion inhibiter of the invention, pipeline elbow is distillated because of wall thickness gradually thinning situation caused by corrosion
Improved.
Contain monoethanolamine, diethanol amine and triethanolamine in corrosion inhibiter of the invention, three kinds of ingredients are obtained according to reaction
Determining ratio, moreover it is possible to effectively overcome in the prior art, the medicament being easy to appear when with single hydramine as corrosion inhibiter is effective
The problem of ingredient is low, usage amount is big, single effect, after it can be seen that injection corrosion inhibiter of the present invention in table 1, table 2, in device
Fe2+Concentration, pH value and elbow wall thickness are held in a more stable range.
Glycerine has certain corrosion inhibition in corrosion inhibiter of the invention；Citric acid can be used as cleaning agent, device capable of washing
The preliminary fouling of the inside, prevents from blocking.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (7)
1. a kind of reformer corrosion inhibiter, which is characterized in that the corrosion inhibiter includes amine complexing agent, and the amine complexing agent is by one
40~55 weight % of ethanol amine, 30~45 weight % of diethanol amine, 10~20 weight % of triethanolamine and synergist composition, it is described
The weight proportion of synergist and the amine complexing agent is 1:1~2, and the synergist includes glycerine and citric acid, glycerine with
The weight proportion of citric acid is 1:1~3；
The preparation method of the reformer corrosion inhibiter, comprising the following steps: take ethylene oxide and ammonia, ethylene oxide and ammonia
The ratio between the amount of substance be 1:4~5, reacted under the conditions of temperature-pressure, obtain amine complexing agent.
2. reformer corrosion inhibiter according to claim 1, which is characterized in that the weight proportion of glycerine and citric acid
For 1:1.
3. reformer corrosion inhibiter according to claim 1, which is characterized in that before reaction, dissolve ammonia in water, ammonia
Concentration in water is 50~70%.
4. reformer corrosion inhibiter according to claim 1, which is characterized in that when ethylene oxide and ammonia react, setting
The pressure of reaction is 15~20MPa, and keeping the temperature of reaction is 130~180 DEG C, is reacted 2 hours.
5. reformer corrosion inhibiter according to claim 4, which is characterized in that when ethylene oxide and ammonia react, setting
The pressure of reaction is 16MPa, and keeping the temperature of reaction is 150 DEG C, is reacted 2 hours.
6. described in any item reformer corrosion inhibiter according to claim 1~5, which is characterized in that ammonia is anti-with ethylene oxide
After the completion of answering, synergist is added into resulting amine complexing agent, the synergist of addition and the mass ratio of amine complexing agent are 1:1~2.
7. reformer corrosion inhibiter according to claim 6, which is characterized in that the synergist of addition include glycerine with
The weight proportion of citric acid, glycerine and citric acid is 1:1~3.
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| CN108263940B (en) * | 2018-01-29 | 2020-04-07 | 陈爱珍 | Use method of device for cleaning escalator |
| CN110747002B (en) * | 2019-11-13 | 2021-06-15 | 上海贵通新材料科技有限公司 | Coking corrosion inhibitor |
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| CN1436164A (en) * | 2000-06-09 | 2003-08-13 | 巴斯福股份公司 | Method for producing alkanolamines |
| CN1597900A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Cleaning-rust-proof dual functional cleaning agent |
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