阅读说明：本技术 有机中和剂 (Organic neutralizing agent ) 是由 徐文忠 于 2019-09-18 设计创作，主要内容包括：本发明公开了一种有机中和剂,其按重量份数计主要包括下述组分：均三嗪基超支化大分子化合物30～50份,木质素磺酸盐2～5份,乙醇胺15～20份,乙酸2～5份,乙酸钠0.5～1份,水35～60份。本发明所述有机中和剂,利用均三嗪基超支化大分子化合物中和炼油体系中的硫化氢,木质素磺酸盐作为分散剂,乙醇胺中和盐酸,乙酸和乙酸钠控制酸碱平衡增加反应速率,各组分协同作用,中和炼油体系中的硫化氢和盐酸,有效防止金属炼油设备被腐蚀。(The invention discloses an organic neutralizer, which mainly comprises the following components in parts by weight: 30-50 parts of s-triazine hyperbranched macromolecular compound, 2-5 parts of lignosulfonate, 15-20 parts of ethanolamine, 2-5 parts of acetic acid, 0.5-1 part of sodium acetate and 35-60 parts of water. According to the organic neutralizing agent, the s-triazine hyperbranched macromolecular compound is used for neutralizing hydrogen sulfide in an oil refining system, the lignosulfonate is used as a dispersing agent, the ethanolamine is used for neutralizing hydrochloric acid, the acetic acid and the sodium acetate are used for controlling acid-base balance to increase the reaction rate, and the components are synergistic to neutralize the hydrogen sulfide and the hydrochloric acid in the oil refining system, so that metal oil refining equipment is effectively prevented from being corroded.)

1. The organic neutralizer is characterized by mainly comprising the following components in parts by weight: 30-50 parts of s-triazine hyperbranched macromolecular compound, 2-5 parts of lignosulfonate, 15-20 parts of ethanolamine, 2-5 parts of acetic acid, 0.5-1 part of sodium acetate and 35-60 parts of water; wherein the chemical structural formula of the s-triazine hyperbranched macromolecular compound is as follows:

2. The organic neutralizing agent of claim 1, wherein the components consist essentially of, in parts by weight: 35 parts of s-triazine hyperbranched macromolecular compound, 3 parts of lignosulfonate, 18 parts of ethanolamine, 3 parts of acetic acid, 1 part of sodium acetate and 35 parts of water.

3. The organic neutralizing agent according to claim 1, wherein the preparation method of the s-triazine based hyperbranched macromolecular compound mainly comprises the following steps:

Step one, mixing ethanolamine and aqueous solution of quaternary ammonium alkali, slowly adding paraformaldehyde, wherein the molar ratio of the ethanolamine to the paraformaldehyde is 1: 0.8-1: 1.2, the using amount of the aqueous solution of the quaternary ammonium alkali is 0.01-0.1% of the molar amount of the ethanolamine, heating to 70-90 ℃, preserving heat for 5 hours, cooling and drying to obtain 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, wherein the chemical structural formula of the aqueous solution of the quaternary ammonium alkali is as follows:

Step two, mixing 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine and toluenesulfonic acid according to the molar ratio of 1: 3-1: 5, dissolving in toluene, stirring and heating to 120 ℃, preserving heat for 2 hours, and performing rotary evaporation to obtain a generation of hyperbranched molecules, wherein the chemical structural formula of the hyperbranched molecules is as follows:

Step three, mixing the first generation of hyperbranched molecules and toluenesulfonic acid, dissolving the mixture in toluene, stirring, adding 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, wherein the molar ratio of the first generation of hyperbranched molecules, 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine and toluenesulfonic acid is 1:6: 6-1: 8:8, heating to 150 ℃, preserving heat for 2 hours, and performing rotary evaporation to obtain second generation of hyperbranched macromolecules, wherein the chemical structural formula of the second generation of hyperbranched macromolecules is as follows:

And step four, mixing the second-generation hyperbranched molecules and toluenesulfonic acid, dissolving in toluene, stirring, adding 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, heating to 180 ℃, keeping the temperature for 2 hours, and performing rotary evaporation to obtain the s-triazinyl hyperbranched macromolecular compound, wherein the molar ratio of the second-generation hyperbranched molecules, 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine to toluenesulfonic acid is 1:12: 12-1: 15: 15.

4. The organic neutralizing agent of claim 3, wherein the molar ratio of ethanolamine to paraformaldehyde in step one is 1: 1.2.

5. The organic neutralizing agent according to claim 3, wherein the aqueous alkali quaternary ammonium salt solution in the first step is an aqueous octadecyl trimethyl ammonium hydroxide solution having a concentration of 10 to 20% and a content of 0.05% by mole based on the ethanolamine.

6. The organic neutralizing agent of claim 3, wherein the temperature in step one is heated to 80 ℃.

7. The organic neutralizing agent of claim 3, wherein the molar ratio of 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine to toluene sulfonic acid in step two is 1: 3.

8. The organic neutralizing agent of claim 3, wherein the molar ratio of the first generation hyperbranched molecule, 1,3, 5-tris (hydroxyethyl) hexahydros-triazine, to toluene sulfonic acid is 1:6: 6.

9. the organic neutralizing agent of claim 3, wherein the mole ratio of the second-generation hyperbranched molecule in step four, 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine to toluene sulfonic acid is 1:12: 12.

Technical Field

The invention belongs to the field of metal corrosion inhibition, and particularly relates to an organic neutralizer for preventing corrosion of a fractionating tower top and cooling and condensing system equipment of devices such as atmospheric and vacuum, catalytic cracking, coking and the like.

Background

In recent years, with the increasing impurity content of crude oil and the increasing processing amount of high-sulfur high-acid value crude oil, the corrosion problem of oil refining equipment becomes more and more serious, and the safe, stable and long-period operation of the equipment is influenced. No matter which crude oil is processed, low-temperature corrosion occurs at the top of the distillation tower and a condensation system, and the low-temperature corrosion belongs to HCl-H₂S-H₂corrosion of the O system. For many years, neutralizing agents have proven necessary in corrosion control procedures, and existing neutralizing agents include mainly the ammonia class, the base class, and the neutralizing amine class. Although the ammonia neutralizing agent can control serious corrosion caused by acid, the salt generated by the reaction of ammonia and hydrochloric acid is acidic and can also cause corrosion, and an environmental protection organization limits the emission amount of ammonia in the sewage of an oil refinery and also limits the application of the ammonia neutralizing agent; the alkali neutralizing agent is easy to generate side reaction with sodium in residual oil, so that certain limitation exists; the neutralized amine has the capability of neutralizing hydrogen sulfide under low temperature, but the reaction is incomplete and is in equilibrium reversible, and the hydrogen sulfide under higher temperatureCan be released again, and the neutralization effect is influenced.

Disclosure of Invention

An object of the present invention is to solve at least the above problems and to provide at least the advantages described later.

The invention also aims to provide an organic neutralizing agent which utilizes an s-triazine hyperbranched macromolecular compound to neutralize hydrogen sulfide in an oil refining system, lignosulfonate is used as a dispersing agent, ethanolamine is used for neutralizing hydrochloric acid, acetic acid and sodium acetate are used for controlling acid-base balance to increase the reaction rate, and all components have synergistic effect to protect oil refining equipment and prevent corrosion.

To achieve these objects and other advantages in accordance with the present invention, there is provided an organic neutralizing agent comprising in major amounts by weight: 30-50 parts of s-triazine hyperbranched macromolecular compound, 2-5 parts of lignosulfonate, 15-20 parts of ethanolamine, 2-5 parts of acetic acid, 0.5-1 part of sodium acetate and 35-60 parts of water, wherein the chemical structural formula of the s-triazine hyperbranched macromolecular compound is as follows:

Preferably, the components mainly comprise the following components in parts by weight: 35 parts of s-triazine hyperbranched macromolecular compound, 3 parts of lignosulfonate, 18 parts of ethanolamine, 3 parts of acetic acid, 1 part of sodium acetate and 35 parts of water.

Preferably, the preparation method of the s-triazine hyperbranched macromolecular compound mainly comprises the following steps:

Step one, mixing ethanolamine and aqueous solution of quaternary ammonium alkali, slowly adding paraformaldehyde, wherein the molar ratio of the ethanolamine to the paraformaldehyde is 1: 0.8-1: 1.2, the using amount of the aqueous solution of the quaternary ammonium alkali is 0.01-0.1% of the molar amount of the ethanolamine, heating to 70-90 ℃, preserving heat for 5 hours, cooling and drying to obtain 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, wherein the chemical structural formula of the aqueous solution of the quaternary ammonium alkali is as follows:

step two, mixing 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine and toluenesulfonic acid according to the molar ratio of 1: 3-1: 5, dissolving in toluene, stirring and heating to 120 ℃, preserving heat for 2 hours, and performing rotary evaporation to obtain a generation of hyperbranched molecules, wherein the chemical structural formula of the hyperbranched molecules is as follows:

step three, mixing the first generation of hyperbranched molecules and toluenesulfonic acid, dissolving the mixture in toluene, stirring, adding 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, wherein the molar ratio of the first generation of hyperbranched molecules, 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine and toluenesulfonic acid is 1:6: 6-1: 8:8, heating to 150 ℃, preserving heat for 2 hours, and performing rotary evaporation to obtain second generation of hyperbranched macromolecules, wherein the chemical structural formula of the second generation of hyperbranched macromolecules is as follows:

And step four, mixing the second-generation hyperbranched molecules and toluenesulfonic acid, dissolving in toluene, stirring, adding 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, heating to 180 ℃, keeping the temperature for 2 hours, and performing rotary evaporation to obtain the s-triazinyl hyperbranched macromolecular compound, wherein the molar ratio of the second-generation hyperbranched molecules, 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine to toluenesulfonic acid is 1:12: 12-1: 15: 15.

preferably, the molar ratio of ethanolamine to paraformaldehyde in the first step is 1: 1.2.

preferably, the aqueous alkali solution of quaternary ammonium in the first step is an aqueous solution of octadecyl trimethyl ammonium hydroxide, the concentration of the aqueous solution is 10-20%, and the dosage of the aqueous solution is 0.05% of the molar weight of ethanolamine.

Preferably, the temperature in said first step is heated to 80 ℃.

Preferably, the molar ratio of 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine to toluene sulfonic acid in the second step is 1: 3.

Preferably, the molar ratio of the first generation hyperbranched molecule in the third step, 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine and toluene sulfonic acid is 1:6: 6.

Preferably, the molar ratio of the second-generation hyperbranched molecule in the fourth step, 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine and toluenesulfonic acid is 1:12: 12.

1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine reacts with hydrogen sulfide to generate partial branched group substitution, and the generated product is dissolved in water, and the reaction equation is as follows:

The invention at least comprises the following beneficial effects:

Firstly, the invention utilizes s-triazine hyperbranched macromolecular compounds to neutralize hydrogen sulfide in an oil refining system, hyperbranched macromolecules are gradually decomposed in the process of gradually reacting with the hydrogen sulfide, and the generated water-soluble sulfide is easy to remove, has high reaction speed and high efficiency and can not generate reversible reaction under the high-temperature condition; in addition, the hyperbranched macromolecule has a dendritic structure, the functionality is high, chain entanglement is not easy to occur in molecules and among molecules, and the hyperbranched macromolecule has the advantages of low viscosity, high activity and the like;

secondly, the organic neutralizing agent disclosed by the invention is simple in formula, can be used for neutralizing and preventing corrosion of a strong corrosion system of an oil refining chemical device such as crude oil distillation, catalytic cracking, coking and the like by taking lignosulfonate as a dispersing agent, controlling acid-base balance by using hydrochloric acid, acetic acid and sodium acetate in an ethanolamine neutralization system to increase the reaction rate, and taking all components and the s-triazine hyperbranched macromolecular compound as a neutralizing agent, and can be widely applied to industrial production.

additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Detailed Description

The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.

it will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.

It is to be noted that the experimental methods described in the following embodiments are all conventional methods unless otherwise specified, and the reagents and materials are commercially available unless otherwise specified.

< example 1>

An organic neutralizer mainly comprises the following components in parts by weight: 35 parts of s-triazine hyperbranched macromolecular compound, 3 parts of lignosulfonate, 18 parts of ethanolamine, 3 parts of acetic acid, 1 part of sodium acetate and 35 parts of water.

The s-triazine hyperbranched macromolecular compound is a third-generation hyperbranched macromolecule, and the preparation method mainly comprises the following steps:

Step one, mixing ethanolamine and an aqueous octadecyl trimethyl ammonium hydroxide solution, slowly adding paraformaldehyde, heating to 80 ℃, preserving heat for 5 hours, cooling and drying to obtain 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, wherein the molar ratio of the ethanolamine to the paraformaldehyde is 1:1.2, the concentration of the aqueous octadecyl trimethyl ammonium hydroxide solution is 15%, and the dosage of the aqueous octadecyl trimethyl ammonium hydroxide solution is 0.05% of the molar weight of the ethanolamine;

Step two, mixing the 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine with toluenesulfonic acid according to the molar ratio of 1:3, dissolving in toluene, stirring and heating to 120 ℃, preserving heat for 2 hours, and performing rotary evaporation to obtain a first-generation hyperbranched molecule;

Mixing the first generation of hyperbranched molecules and toluenesulfonic acid, dissolving in toluene, stirring, adding the 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine, heating to 150 ℃, keeping the temperature for 2 hours, and performing rotary evaporation to obtain second generation of hyperbranched macromolecules, wherein the molar ratio of the first generation of hyperbranched molecules, 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine and toluenesulfonic acid is 1:6: 6;

And step four, mixing the second-generation hyperbranched molecules and toluenesulfonic acid, dissolving in toluene, stirring, adding the 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine, heating to 180 ℃, keeping the temperature for 2 hours, and performing rotary evaporation to obtain the s-triazine-based hyperbranched macromolecular compound, wherein the molar ratio of the second-generation hyperbranched molecules, the 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine and the toluenesulfonic acid is 1:12: 12.

< example 2>

An organic neutralizer mainly comprises the following components in parts by weight: 50 parts of s-triazine hyperbranched macromolecular compound, 5 parts of lignosulfonate, 15 parts of ethanolamine, 2 parts of acetic acid, 0.5 part of sodium acetate and 60 parts of water.

The s-triazine hyperbranched macromolecular compound is a second-generation hyperbranched macromolecule, and the preparation method mainly comprises the following steps:

Step one, mixing ethanolamine and an aqueous octadecyl trimethyl ammonium hydroxide solution, slowly adding paraformaldehyde, heating to 80 ℃, preserving heat for 5 hours, cooling and drying to obtain 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, wherein the molar ratio of the ethanolamine to the paraformaldehyde is 1:1.2, the concentration of the aqueous octadecyl trimethyl ammonium hydroxide solution is 15%, and the dosage of the aqueous octadecyl trimethyl ammonium hydroxide solution is 0.05% of the molar weight of the ethanolamine;

step two, mixing the 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine with toluenesulfonic acid according to the molar ratio of 1:3, dissolving in toluene, stirring and heating to 120 ℃, preserving heat for 2 hours, and performing rotary evaporation to obtain a first-generation hyperbranched molecule;

and step three, mixing the first generation of hyperbranched molecules and toluenesulfonic acid, dissolving in toluene, stirring, adding the 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine, heating to 150 ℃, keeping the temperature for 2 hours, and performing rotary evaporation to obtain second generation hyperbranched macromolecules, wherein the molar ratio of the first generation of hyperbranched molecules, 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine and toluenesulfonic acid is 1:6: 6.

< example 3>

An organic neutralizer mainly comprises the following components in parts by weight: 30 parts of s-triazine hyperbranched macromolecular compound, 2 parts of lignosulfonate, 20 parts of ethanolamine, 5 parts of acetic acid, 1 part of sodium acetate and 50 parts of water.

The s-triazine hyperbranched macromolecular compound is a generation of hyperbranched molecule, and the preparation method mainly comprises the following steps:

step one, mixing ethanolamine and an aqueous octadecyl trimethyl ammonium hydroxide solution, slowly adding paraformaldehyde, heating to 80 ℃, preserving heat for 5 hours, cooling and drying to obtain 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, wherein the molar ratio of the ethanolamine to the paraformaldehyde is 1:1.2, the concentration of the aqueous octadecyl trimethyl ammonium hydroxide solution is 15%, and the dosage of the aqueous octadecyl trimethyl ammonium hydroxide solution is 0.05% of the molar weight of the ethanolamine;

and step two, mixing the 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine with toluenesulfonic acid according to the molar ratio of 1:3, dissolving in toluene, stirring and heating to 120 ℃, preserving heat for 2 hours, and performing rotary evaporation to obtain the first-generation hyperbranched molecule.

< comparative example 1>

An organic neutralizer mainly comprises the following components in parts by weight: 35 parts of 1,3, 5-tris (hydroxyethyl) hexahydro-s-triazine, 3 parts of lignosulfonate, 18 parts of ethanolamine, 3 parts of acetic acid, 1 part of sodium acetate and 35 parts of water.

< comparative example 2>

An organic neutralizer mainly comprises the following components in parts by weight: 3 parts of lignosulfonate, 60 parts of ethanolamine, 3 parts of acetic acid, 1 part of sodium acetate and 35 parts of water.

< test of neutralizing Effect of hydrochloric acid >

an equal amount of the organic neutralizing agent prepared in the above example and comparative example was sampled and placed in an Erlenmeyer flask, respectively, ethanol was added to the Erlenmeyer flask to dissolve the samples, 0.1% bromophenol blue-ethanol indicator was added dropwise to the Erlenmeyer flask, the amount of consumed hydrochloric acid was marked by titration with 0.1mol/L hydrochloric acid-ethanol standard solution until the yellow color just appeared, and the neutralization value (N) of each sample was calculated and expressed in mg NaOH/g:

N＝(ΔV×0.1×40.01)/m，

In the formula: Δ V is the number of milliliters, ml, of hydrochloric acid consumed; m is the weight, g, of the sample.

TABLE 1

As can be seen from Table 1, the organic neutralizing agent of the formulation of example 1 has the highest neutralization value and the best neutralization effect on hydrochloric acid, and is the preferred formulation for industrial products; in comparative example 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine which is not hyperbranched has a certain neutralization effect, but because hyperbranched molecules have high functionality and strong activity, the neutralization value is higher and the neutralization effect is better in each example compared with comparative example 1; in comparative example 2, since hydrochloric acid was neutralized only with ethanolamine, the resulting salt was also somewhat acidic, and thus the neutralization value was low.

< test for neutralizing Effect of Hydrogen sulfide >

the organic neutralizer prepared in the above examples and comparative examples was taken as a sample, and added to a flat-bottomed flask containing sulfur-containing oil, the stopper was plugged, shaken vigorously up and down 200 times, heated to 100 ℃. + -. 2 ℃, and then the hydrogen sulfide content in the bottle mouth was measured in ppm by using "method for measuring hydrogen sulfide that can escape from the effluent".

TABLE 2

as can be seen from Table 2, the organic neutralizing agent of the formulation of example 1 neutralized hydrogen sulfide the best and was the preferred formulation for commercial products; compared with examples 1, 2 and 3, the hyperbranched degree is higher, the functionality of the compound is higher, the activity is higher, and the neutralization effect on hydrogen sulfide is better; in comparative example 1,3, 5-tri (hydroxyethyl) hexahydro-s-triazine which is not hyperbranched has a certain effect of neutralizing hydrogen sulfide, but the effect of neutralizing hydrogen sulfide is poorer than that of each example; in comparative example 2, the reaction of ethanolamine with hydrogen sulfide is not complete and is equilibrium-reversible, and at higher temperature, hydrogen sulfide is released again, so that the neutralization effect is deteriorated.

< test of Corrosion inhibition Effect >

Taking the organic neutralizing agent prepared in the above examples and comparative examples as a sample, HCl (1000ppm) + H₂Pouring a 4L corrosion medium consisting of an S (100ppm) aqueous solution into a container, taking each sample, respectively adding the samples into the container, suspending a cleaned and weighed A20 carbon steel test piece in the corrosion medium at 80 +/-2 ℃, rotating the test piece at a speed of 45 revolutions per minute, taking out the test piece after 72 hours, cleaning and weighing, taking the corrosion medium without the added sample as a blank control group, and calculating the corrosion inhibition rate according to the following formula:

in the formula: Δ G₀G, the mass difference between the front and the back of the test piece of the blank control group is g; Δ G₁G, the mass of the test piece before and after the test is poor after the sample is added.

TABLE 3

	Example 1	example 2	Example 3	Comparative example 1	comparative example 2
						Inhibition ratio (%)	95.5	93.7	91.8	85.2	84.6

As can be seen from table 3, since the branched macromolecule has a dendritic structure, has high functionality, is not easy to generate chain entanglement in molecules and between molecules, has high activity, and has good film forming property, the organic neutralizing agents prepared in examples 3, 2 and 1 have gradually increased thickness of the protective film formed by deposition of the branched molecules on the metal surface as the branching degree becomes larger, so that the corrosion inhibition rate is gradually increased; for comparative example 1 and comparative example 2, the corrosion inhibition rate was poor because the molecular weight was small, the film forming property was poor, and a protective film could not be formed on the metal surface.

The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be apparent to those skilled in the art.

While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the examples shown and described without departing from the generic concept as defined by the claims and their equivalents.