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CN117448037B - Scale inhibitor for high-temperature oil refining system and preparation method and application thereof - Google Patents

Scale inhibitor for high-temperature oil refining system and preparation method and application thereof Download PDF

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Publication number
CN117448037B
CN117448037B CN202311429887.1A CN202311429887A CN117448037B CN 117448037 B CN117448037 B CN 117448037B CN 202311429887 A CN202311429887 A CN 202311429887A CN 117448037 B CN117448037 B CN 117448037B
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scale inhibitor
triazole
oil refining
refining system
temperature oil
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CN117448037A (en
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初志永
胡云霞
刘廷亮
刘其春
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Shandong Aorun Chemical Technology Co ltd
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Shandong Aorun Chemical Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6852Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from hydroxy carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G75/00Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention provides a scale inhibitor for a high-temperature oil refining system, and a preparation method and application thereof, wherein the scale inhibitor comprises a triazole polymer obtained by esterifying and polymerizing 1-acetic acid-4- (1-hydroxycyclopentyl) -1,2, 3-triazole and purine containing hydroxyl, wherein the triazole polymer can form a micro cross-linked network in an oil system, form capsules with oxygen-containing compounds, and is dissolved in oil to prevent oxidation and condensation, thereby inhibiting scale deposition; the hydroxyl-containing purine can form a protective film layer on the side surface of equipment, and reduce or eliminate corrosion to the equipment. When hydroxyl groups in the scale inhibitor are oxidized at high temperature, carboxyl groups can form chelates with metal ions such as iron, copper and the like, so that the chelates lose the catalytic capability on polymerization reaction, and the generation of scale is reduced.

Description

Scale inhibitor for high-temperature oil refining system and preparation method and application thereof
Technical Field
The invention relates to the field of scale inhibition and corrosion prevention, in particular to a scale inhibitor for a high-temperature oil refining system, a preparation method and application thereof.
Background
The petroleum processing is a continuous large-scale production process, the processed grafts are crude oil or oil products containing impurities, and almost all the oil products need to be heated or cooled according to the requirements of the processing technology, and some settings are heated to high temperature of about 500 ℃. Thus, a layer of scale, either hard or soft, is formed on the surface of the refinery and pipeline. Such scaling phenomena are very common in the oil refining industry, such as heat exchangers, coolers, reactors, reboilers, heating furnaces, etc., during which the scale reduces the internal diameter of equipment, pipes, valves, reduces the process flow and heat transfer, limits the throughput of the plant, leads to increased power consumption, decreases the yield of the final product, shortens the start-up cycle, increases the maintenance costs, even presents huge accidents, affects the safe operation of the production plant, and the losses of scale to the production are huge. It is counted that more than 90% of the heat exchangers in refineries have different degrees of fouling problems. The loss of scaling in the United states oil refining industry has been estimated from energy consumption, yield reduction, and maintenance costs, and the like, and the loss of scaling-related whole-world oil refining industry costs up to $13 billion per year.
The scale can be divided into two types, namely organic scale and inorganic scale, and the chemical reaction of the organic scale on oil refining equipment and pipelines is formed into 4 types of free radical chain reaction, asphaltene condensation reaction, thermal conversion reaction and polymerization reaction, and in the high-temperature heavy oil processing device, the organic scale is mainly generated by the asphaltene condensation reaction and the thermal conversion reaction; the main reasons for the formation of inorganic scale are precipitation of salt compounds and deposition of impurity particles, the salt compounds are mainly brought by crude oil, and then certain acidic substances exist in the crude oil or the oil, which can cause certain corrosion to equipment and pipelines in the processes of storage, transportation and processing, corrosion products are generated, and inorganic salts and corrosion products carried by the crude oil can be precipitated and adhered to the surfaces of the equipment or the pipelines under certain conditions to form the inorganic scale. Since most of the inorganic salts are concentrated into normal slag and reduced slag during petroleum processing, inorganic salt precipitation is an important cause of these heavy oil fouls.
Thus, the problem of fouling of petroleum processing equipment and pipelines has become a major obstacle affecting the safe, smooth, long-term, full-load production operation of the apparatus, and it has been an urgent task to study scale inhibitors that are effective in preventing or reducing fouling.
Disclosure of Invention
Aiming at the scale formation reason, the invention provides a scale inhibitor for a high-temperature oil refining system, a preparation method and application thereof.
A scale inhibitor for a high-temperature oil refining system comprises 20-35% of a detergent dispersant, 1-8% of a corrosion inhibitor, 0.5-2% of an antioxidant and the balance of an organic solvent; wherein the detergent dispersant is triazole polymer prepared by taking 1-acetic acid-4- (1-hydroxycyclopentyl) -1,2, 3-triazole (CAS: 1402447-07-7) with a structure shown in formula I as a polymerization monomer, and the corrosion inhibitor is purine containing hydroxyl;
in some embodiments of the invention, the hydroxyl-containing purine is at least one of adenine nucleoside and arabinoside.
In some embodiments of the present invention, the process for preparing the triazole polymer comprises the steps of: dissolving 1-acetic acid-4- (1-hydroxycyclopentyl) -1,2, 3-triazole in an organic solvent 1 under normal pressure, adding a catalyst, carrying out reflux reaction for 3-5h at 130-160 ℃, cooling the system, adding a salt solution for washing and layering, drying the organic phase to remove the solvent, dissolving with an organic solvent 2, and filtering to obtain the solution of the triazole polymer.
In some embodiments of the present invention, the organic solvent 1 is at least one of ethanol, dimethyl sulfoxide, dichloromethane, toluene, and xylene when preparing the triazole polymer.
In some embodiments of the present invention, the catalyst in preparing the triazole polymer is at least one of aluminum chloride, boron fluoride, stannous chloride, zinc chloride, titanium tetrachloride.
In some embodiments of the invention, the catalyst is added in an amount of 0.5 to 1% by mass of the total system of reactions in the preparation of the triazole polymer.
In some embodiments of the present invention, the organic solvent 2 is at least one of 1, 2-dimethoxypropane, dimethoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran, and dimethyltetrahydrofuran in preparing the triazole polymer.
In some embodiments of the present invention, the antioxidant is at least one of phosphites, which may be, but is not limited to: tris (nonylphenyl) phosphite (TNP), tris (2, 4) -di-t-butylphenyl) phosphite (TBP), distearyl Pentaerythritol Diphosphite (DPD), tetrakis (2, 4-di-t-butylphenyl) -4,4' -biphenylenediphosphate, and the like.
In some embodiments of the invention, the solvent is a non-polar hydrocarbon solvent such as toluene, xylene, petroleum ether, paraffin oil, diesel oil, kerosene, and the like.
The mixing mass ratio of the purine to the triazole polymer in the scale inhibitor is 1-8:20-35. The purine is taken as a small molecular substance, and a protective film can be formed on the inner side of the pipe wall in an oil refining system by adding a proper amount of purine, so that the coke produced by crude oil at high temperature is prevented from being adsorbed and deposited on the pipe wall; however, if the dosage is too large, a micelle is formed with the triazole polymer, so that the adsorption and dispersion of the triazole polymer on pollutant particles are affected, and finally the scale inhibitor has a weakened protection effect on an oil refining system. The proportion can keep balance of the scale inhibitor effect, and the scale inhibitor effect of the whole device can be influenced by deviating from the proportion.
The scale inhibitor is prepared by mixing the detergent dispersant, the corrosion inhibitor, the antioxidant and the solvent according to a proper proportion, and is applied to a high-temperature oil refining system, wherein the application addition amount is 50-150ppm.
The beneficial effects are that: compared with the prior art, the scale inhibitor provided by the invention has the following advantages:
1, the hydroxyl-containing purine is alkalescent, can neutralize acidic substances in crude oil, is not strong in alkalinity and does not have corrosiveness to equipment, a protective film layer can be formed on the inner side of the device, corrosion of other substances in an oil refining system to the equipment is reduced or eliminated, and if hydroxyl groups contained in the hydroxyl-containing purine are oxidized at high temperature in the system, carboxyl groups can be finally formed to chelate metal ions such as iron, copper and the like, so that the carboxyl groups lose catalytic capability to polymerization reaction, the formation of organic high polymers is inhibited, and further the production of scale is reduced;
2, the triazole polymer molecular chain can form a micro cross-linking structure through hydrogen bonds among triazole rings, can well adsorb oil coke and other pollutants in a system, and form a 'load micelle', so that the pollutant particles are dispersed and suspended in oil, and are prevented from settling to form oil dirt;
3, in the scale inhibitor, one component can realize multiple effects, so that the production cost is reduced, the action efficiency is improved, and the heat exchange efficiency of the heat exchanger and the relative stability of pressure drop in the heat exchanger are ensured; and the triazole polymer contained in the composition is easy to biodegrade and is environment-friendly.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation of the triazole polymers used in the scale inhibitor is exemplified below:
triazole polymer-1
7.0g of 1-acetic acid-4- (1-hydroxycyclopentyl) -1,2, 3-triazole is dissolved in 50ml of dimethyl sulfoxide under normal pressure, 0.31g of stannous chloride is added, reflux reaction is carried out for 5 hours at 130 ℃, after the system is cooled, sodium chloride solution is added for washing and layering, organic phase is dried to remove solvent, and then dimethoxy methane is used for dissolving and filtering to obtain the solution of the triazole polymer.
Triazole polymer-2
10.0g of 1-acetic acid-4- (1-hydroxycyclopentyl) -1,2, 3-triazole is dissolved in 100ml of dimethyl sulfoxide under normal pressure, 0.60g of stannous chloride is added, reflux reaction is carried out for 3 hours at 150 ℃, after the system is cooled, sodium chloride solution is added for washing and layering, organic phase is dried to remove solvent, and then dimethoxy methane is used for dissolving and filtering to obtain the solution of the triazole polymer.
The detergent dispersant, the corrosion inhibitor, the antioxidant and the solvent are uniformly mixed to form the scale inhibitor, and the specific selection and the use proportion of the components in each example and comparative example are shown in Table 1:
the scale inhibitor obtained by mixing the raw materials in proportion according to the selection of the raw materials in Table 1 is applied to a heavy oil catalytic device of a petrochemical company in an addition amount of 100ppm, and the specific cases are as follows:
as can be seen from the data in table 2, the scale inhibitor provided by the invention can effectively reduce the viscosity of the slurry oil and the slurry oil quantity thrown outward, and can improve the yield of light oil and the circulation quantity of the slurry oil; in the same cycle period, the pressure drop at the inlet and outlet of the slurry oil heat exchanger is not increased along with the increase of the operation period, and is reduced by at least 0.052MPa, which indicates that the light of the outlet of the slurry oil pump and the light beam inner wall smoothness and the flow area of the heat exchanger system are improved; in the heat exchanger structure. Under the condition that the fluid performance and the operation parameters are not changed greatly, the total heat transfer coefficient of the heat exchanger is improved, which indicates that the dirt on the inner wall of the heat exchanger is effectively inhibited or/and removed, and the data of comparative examples 1-2 show that the use ratio of the triazole polymer and the purine has a certain negative influence on the use effect of the dirt inhibitor: the excessive use of purine can not only help to reduce the pressure drop and heat transfer coefficient of the inlet and outlet of the heat exchanger, but also can cause obstruction. From the results of comparative example 3, it is understood that a general low molecular weight polyamide compound cannot be used as an oil slurry scale inhibitor instead of the triazole polymer and a similar treatment effect is obtained.
In conclusion, the scale inhibitor provided by the invention can realize ideal scale inhibition effect in a high-temperature oil refining system, improves the crude oil processing efficiency, and has good economic benefit in the high-temperature oil refining field.

Claims (6)

1. The scale inhibitor for the high-temperature oil refining system is characterized by comprising 20-35% of a detergent dispersant, 1-8% of a corrosion inhibitor, 0.5-2% of an antioxidant and the balance of an organic solvent in percentage by mass; the detergent dispersant is triazole polymer prepared by taking 1-acetic acid-4- (1-hydroxycyclopentyl) -1,2, 3-triazole with a structure shown in formula I as a polymerization monomer, and the corrosion inhibitor is purine containing hydroxyl; the hydroxyl-containing purine is at least one of adenine nucleoside and arabinoside;
the method comprises the steps of carrying out a first treatment on the surface of the The preparation process of the triazole polymer comprises the following steps: dissolving 1-acetic acid-4- (1-hydroxycyclopentyl) -1,2, 3-triazole in an organic solvent 1 under normal pressure, adding a catalyst, and refluxing at 130-160 DEG CReacting for 3-5h, cooling the system, adding a salt solution to wash and delaminate, drying an organic phase to remove a solvent, dissolving the organic phase by using an organic solvent 2, and filtering to obtain a solution of the triazole polymer; wherein the catalyst is at least one of aluminum chloride, boron fluoride, stannous chloride, zinc chloride and titanium tetrachloride; the addition amount of the catalyst accounts for 0.5-1% of the total system mass of the reaction.
2. The scale inhibitor for high temperature oil refining system according to claim 1, wherein the organic solvent 1 is at least one of ethanol, dimethyl sulfoxide, methylene chloride, toluene, and xylene.
3. The scale inhibitor for high temperature oil refining system according to claim 1, wherein the organic solvent 2 is at least one of 1, 2-dimethoxypropane, dimethoxymethane, ethylene glycol dimethyl ether, tetrahydrofuran and dimethyltetrahydrofuran.
4. The scale inhibitor for high-temperature oil refining system according to claim 1, wherein the antioxidant is at least one of phosphite esters.
5. The scale inhibitor for high temperature oil refining system according to claim 1, wherein the organic solvent is at least one of toluene, xylene, petroleum ether, paraffin oil, diesel oil, and kerosene.
6. The scale inhibitor for high temperature oil refining system according to any one of claims 1 to 5, wherein the addition amount is 50 to 150ppm.
CN202311429887.1A 2023-10-31 2023-10-31 Scale inhibitor for high-temperature oil refining system and preparation method and application thereof Active CN117448037B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292425A (en) * 1992-10-21 1994-03-08 Betz Laboratories, Inc. Use of the reaction products of polyalkenylsuccinimides, triazoles, and aldehydes as anti foulants in hydrocarbon process media
CN108441253A (en) * 2018-01-23 2018-08-24 中海油天津化工研究设计院有限公司 A kind of antisludging agent for coker gasoline pipeline
CN110699117A (en) * 2019-11-04 2020-01-17 山东益丰生化环保股份有限公司 Multifunctional oil slurry scale inhibitor and preparation method thereof
WO2020143040A1 (en) * 2019-01-11 2020-07-16 黄华成 Tryptophan derivative and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5292425A (en) * 1992-10-21 1994-03-08 Betz Laboratories, Inc. Use of the reaction products of polyalkenylsuccinimides, triazoles, and aldehydes as anti foulants in hydrocarbon process media
CN108441253A (en) * 2018-01-23 2018-08-24 中海油天津化工研究设计院有限公司 A kind of antisludging agent for coker gasoline pipeline
WO2020143040A1 (en) * 2019-01-11 2020-07-16 黄华成 Tryptophan derivative and use thereof
CN110699117A (en) * 2019-11-04 2020-01-17 山东益丰生化环保股份有限公司 Multifunctional oil slurry scale inhibitor and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
国内间冷开式循环冷却水系统阻垢缓蚀剂工程应用进展;刘小雷等;水处理技术;20170531(05);第27-30页 *

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