CN110699116A - Coal tar coking inhibitor and preparation method and application thereof - Google Patents
Coal tar coking inhibitor and preparation method and application thereof Download PDFInfo
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- CN110699116A CN110699116A CN201910984524.1A CN201910984524A CN110699116A CN 110699116 A CN110699116 A CN 110699116A CN 201910984524 A CN201910984524 A CN 201910984524A CN 110699116 A CN110699116 A CN 110699116A
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- 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
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Abstract
The invention provides a coal tar coking inhibitor which comprises the following raw materials in percentage by weight: 25-40% of asphaltene dispersant, 10-25% of antioxidant, 10-25% of free radical deactivator, 1-5% of metal surface deactivator and 30-40% of solvent. The invention also provides a preparation method and application of the coal tar coking inhibitor. The coal tar coking inhibitor has simple processing technology, and can effectively inhibit and delay coking of high-temperature equipment such as a heating furnace, a heat exchanger, a reactor and the like in the high-temperature processing process by adding the coal tar coking inhibitor accounting for 0.03-0.05% of the weight, thereby prolonging the start-up period of the device.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a coal tar coking inhibitor for preventing coal tar from coking, and a preparation method and application thereof.
Background
Coal tar is a main raw material in the coal chemical industry, is a black or black brown viscous liquid obtained in the coal coking process, namely a black liquid extracted after coal carbonization, and can be divided into low-temperature coal tar (450-. The coal tar is quite complex in component, mainly comprises polycyclic aromatic compounds, has low content of alkyl aromatic hydrocarbons, more high-boiling-point components and good thermal stability, wherein the content of naphthalene is high, and the relative content of the rest is low, and the coal tar mainly comprises 1-methylnaphthalene, 2-methylnaphthalene, acenaphthene, fluorene, dibenzofuran, anthracene, phenanthrene, quinoline, pyrene and the like. The properties of each component of the tar are different, but the properties are similar to those of more components, various fractions are required to be cut by adopting a distillation method, single-component products to be extracted, such as phenol, naphthalene, anthracene and the like, are concentrated and concentrated into corresponding fractions, then physical and chemical methods are further utilized for separation, and the fraction before 170 ℃ is separated to be light oil; the fraction at 170-210 ℃ is mainly phenol oil; the fraction at 210-230 ℃ is mainly naphthalene oil; the fraction at 230-300 ℃ is mainly wash oil; the fraction at 280-360 ℃ is mainly anthracene oil; the primary distillation point of the dianthracene oil fraction is 310 ℃, and the distillation point of the dianthracene oil fraction is 400 ℃. In most cases, the method is adopted for separation and purification, and then the tar fractions are further processed to separate out various products.
In recent years, with continuous heavy and inferior crude oil in petrochemical industry, the production of light fuel oil by hydrogenation of partial or whole fractions of coal tar has attracted more and more attention, but due to the complexity of components of coal tar, coal tar contains many impurities which have adverse effects on subsequent processing and utilization, particularly colloid and asphaltene components in coal tar, and in the hydrogenation reaction process, as the asphaltene is composed of macromolecular hydrocarbons and non-hydrocarbon substances with large molecular weight and complex structure, the aromaticity is the largest, coking of high-temperature equipment such as a heating furnace, a heat exchanger and a reactor, carbon deposition and inactivation of catalysts are easily caused, even the reactor and pipelines are seriously blocked, and the start-up period is greatly influenced. Therefore, reducing or inhibiting the content of asphaltenes in coal tar is a key technology for the deep processing of coal tar.
Disclosure of Invention
In order to solve the problems, the invention provides a coal tar coking inhibitor for preventing and inhibiting coal tar coking, which has simple process and does not need specific reaction equipment and harsh reaction conditions, the prepared coal tar coking inhibitor can effectively inhibit the polymerization and coking processes of unsaturated matters in the coal tar at high temperature, can change the structures of scales and coked matters, is loose and easy to remove, and inhibits and delays coking of high-temperature equipment such as a heating furnace, a heat exchanger, a reactor and the like, thereby prolonging the start-up period of the device.
The technical scheme is realized as follows:
the invention discloses a coal tar coking inhibitor which comprises the following raw materials in percentage by weight: 25-40% of asphaltene dispersant, 10-25% of antioxidant, 10-25% of free radical deactivator, 1-5% of metal surface deactivator and 30-40% of solvent.
Further, the asphaltene dispersant is one or more of long-chain alkyl acid with an amphiphilic molecular structure and sodium salt thereof, long-chain olefine acid, long-chain dimer acid, long-chain alkyl alcohol, long-chain alkylphenol, long-chain alkylamine, enamine and polymer thereof, and long-chain alkyl acid polyol monoester.
Further, the antioxidant includes one or more of aromatic amines, hindered phenols, organic phosphoric acid/phosphorous acid mono-or diesters, and the like.
Further, the free radical deactivator comprises one or more of naphthenic base aromatic hydrocarbon compounds and phenolic polymerization inhibitors.
Further, the metal surface passivating agent is one or more of a nitrogen-containing heterocyclic compound benzotriazole and derivatives thereof, imidazoline and derivatives thereof.
Further, the solvent is one or more of benzene, toluene, xylene, trimethylbenzene, kerosene, light diesel oil and wash oil.
The preparation method of the coal tar coking inhibitor comprises the following steps:
1) preparing materials according to a set mass percentage in advance;
2) adding a certain amount of solvent into a blending device according to a certain proportion, and starting a stirrer for stirring;
3) and sequentially adding solid raw materials in an antioxidant, a free radical deactivator, a metal surface passivator and an asphaltene dispersant, heating to a temperature T required by blending, adding liquid raw materials in the antioxidant, the free radical deactivator, the metal surface passivator and the asphaltene dispersant after uniform mixing, and cooling to below 35 ℃ after uniform mixing to obtain the coal tar coking inhibitor.
In the preparation method of the coal tar coking inhibitor, the temperature T is 45-180 ℃, and the stirring speed is 80-500 r/min.
In the application of the coal tar coking inhibitor, the coal tar coking inhibitor is added into a heating homogenizer with coal tar according to the proportion of 0.03-0.05 percent of the total weight of the coal tar.
The coal tar coking inhibitor, the preparation method and the application thereof have the following beneficial technical effects:
the coal tar coking inhibitor provided by the invention takes asphaltene dispersant, antioxidant, free radical deactivator, metal surface passivator and solvent as main raw materials, and the specific preparation method is as follows: adding a certain amount of solvent into a blending device according to a proportion, starting a stirrer for stirring, sequentially adding solid raw materials in an antioxidant, a free radical deactivator, a metal surface passivator and an asphaltene dispersant, heating to a blending required temperature T, adding liquid raw materials in the antioxidant, the free radical deactivator, the metal surface passivator and the asphaltene dispersant after uniform mixing, and cooling to below 35 ℃ after uniform mixing to obtain the coal tar coking inhibitor.
The coal tar coking inhibitor provided by the invention has the following use effect simulation test: adding a certain amount of coal tar into a heating homogenizer, then adding the coal tar coking inhibitor according to different proportions of 0.03-0.05% (mass ratio), heating, stirring at 2000-5000r/min, performing a simulated scaling test at 360 ℃ for 72 hours at the same flow rate, comparing with a blank coal tar simulated scaling test without adding the agent, and analyzing and detecting the scaling and coking conditions of the coal tar with the agent and the coal tar without the agent in a scaling pipe of a test device. The coal tar coking inhibitor has obvious beneficial effects on high-temperature coal tar and medium-temperature coal tar.
Drawings
FIG. 1 is a coal tar coking inhibitor laboratory blending device;
FIG. 2 is a coal tar scaling simulation test device.
As shown in figure 1, the coal tar coking inhibitor laboratory blending device comprises: a constant temperature oil bath pot 1, a constant pressure funnel 2, a stirrer 3, a thermometer 4, a condenser 5 and a three-neck flask 6.
As shown in fig. 2, the coal tar scaling simulation test device comprises: the device comprises a heating homogenizer 7, a micro-metering pump 8, a coal tar inlet temperature controller 9, a coal tar scaling pipe heating furnace temperature controller 10, a coal tar scaling pipe 11, a coal tar scaling pipe heating furnace 12, a coal tar outlet temperature display 13, a heat exchanger 14 and a receiving tank 15.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the scope of the present invention is not limited thereto.
In the first embodiment, referring to fig. 1 and 2:
the raw material formula of the coal tar coking inhibitor is as follows:
asphaltene dispersant: 15 g of lauric acid and 15 g of oleic acid
Antioxidant: 2-Methylenebis (4-methyl-6-tert-butylphenol) 15 g
Radical deactivator: tetralin 5 g, p-tert-butylcatechol 10 g
Metal surface passivator: 5 g of 5-methylbenzotriazole
Solvent: benzene 15 g, mixed xylene 20 g
The preparation method of the coal tar coking inhibitor comprises the following steps:
(1) adding 15 g of solvent benzene and 20 g of mixed xylene into a three-neck flask provided with a stirring device, a reflux condenser pipe and a thermometer, then respectively adding 15 g of 2-methylene bis (4-methyl-6-tert-butylphenol), 5 g of 5-methyl benzotriazole and 10 g of p-tert-butyl catechol, starting a stirrer to stir (the rotating speed is 180 r/min), heating, and carrying out reflux dissolution at the temperature of 85 ℃ to form a uniform solution.
(2) And continuously adding 5 g of tetrahydronaphthalene, 15 g of lauric acid and 15 g of oleic acid into the flask to fully and uniformly mix the materials, cooling the mixture to below 35 ℃, and filtering the mixture to obtain the coal tar coking inhibitor.
Has the following beneficial technical effects: the coal tar A in the example is medium temperature coal tar from Yulin A company in Shaanxi, the addition amount of the coal tar coking inhibitor is 0.04% (mass ratio), the test device runs for 72 hours at 360 ℃, and the condition of the coal tar scaling pipe is observed.
TABLE 1 coal tar A pre-and post-dosing test data
As can be seen from the table above, after 72 hours, the weight of the blank coal tar scaling pipe is increased by 78.9g, the added coal tar is only increased by 31.4g, the scaling amount of the blank coal tar is 2.51 times of that of the added coal tar, and the coal tar coking inhibitor provided by the invention is added, so that the start-up period of a medium-temperature coal tar hydrogenation device can be prolonged by more than 1.5 times by eliminating other influence factors, and the adding effect is quite obvious.
Example two, with reference to fig. 1 and 2:
the raw material formula of the coal tar coking inhibitor is as follows:
asphaltene dispersant: 30 g of coconut oil acid monoglyceride and 10 g of octadecyl amine;
antioxidant: 10 g of N, N' -xylyl-p-phenylenediamine (mixture);
radical deactivator: 7 g of tetrahydronaphthalene and 5 g of p-tert-butylcatechol;
metal surface passivator: 3 g of oleic imidazoline derivative;
solvent: mixed xylene 20 g and mixed trimethylbenzene 15 g.
The preparation method of the coal tar coking inhibitor comprises the following steps:
(1) 20 g of solvent mixed xylene and 15 g of mixed trimethylbenzene are added into a three-neck flask provided with a stirring device, a reflux condenser tube and a thermometer, then 10 g of N, N' -ditolyl-p-phenylenediamine (mixture), 10 g of octadecyl amine and 5 g of p-tert-butyl catechol are respectively added, stirring is started (the rotating speed is 120 r/min), and the mixture is dissolved at the temperature of 100 ℃ to form a uniform solution.
(2) 7 g of tetrahydronaphthalene, 3 g of oleic imidazoline derivatives and 30 g of coconut oil acid monoglyceride are continuously added into a flask to be fully and uniformly mixed, the temperature is reduced to below 35 ℃, and the coal tar coking inhibitor can be obtained by filtering.
Has the following beneficial technical effects: the coal tar B in the example is derived from high-temperature coal tar of Henan B company, the addition amount of the coal tar coking inhibitor is 0.05 percent (mass ratio), the test device runs for 72 hours at 360 ℃, and the condition of the coal tar scaling tube is observed.
TABLE 2 coal tar B pre-and post-dosing test data
As can be seen from the above table 2, after 72 hours, the weight of the blank coal tar scaling pipe is increased by 89.6g, the added coal tar is only increased by 37.1g, and the scaling amount of the blank coal tar is about 2.42 times of that of the added coal tar, which shows that the working period of the high-temperature coal tar hydrogenation device can be prolonged by more than 1.4 times by adding the coal tar coking inhibitor of the invention and excluding other influencing factors, and the adding effect is very obvious.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which disclosure and teachings of the above specification, and the present invention is intended to be limited only by the following examples and its advantages. And the present invention is not limited to the specific embodiments and experimental results disclosed and described above, and therefore, some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (9)
1. The coal tar coking inhibitor is characterized by comprising the following raw materials in percentage by weight: 25-40% of asphaltene dispersant, 10-25% of antioxidant, 10-25% of free radical deactivator, 1-5% of metal surface deactivator and 30-40% of solvent.
2. The coal tar coking inhibitor according to claim 1, wherein the asphaltene dispersant is one or more of long-chain alkyl acid and sodium salt thereof, long-chain olefinic acid, long-chain dimer acid, long-chain alkyl alcohol, long-chain alkylphenol, long-chain alkylamine, enamine and polymer thereof, and long-chain alkyl acid polyol monoester having amphiphilic structure.
3. The coal tar coking inhibitor according to claim 1, wherein the antioxidant comprises one or more of aromatic amines, hindered phenols, organic phosphoric acid/phosphorous acid mono-or diesters, and the like.
4. The coal tar coking inhibitor according to claim 1 wherein the free radical deactivator comprises one or more of a cycloalkylaromatic compound or a phenolic inhibitor.
5. The coal tar coking inhibitor according to claim 1, wherein the metal surface passivating agent is one or more of a nitrogen-containing heterocyclic compound benzotriazole and derivatives thereof, imidazoline and derivatives thereof.
6. The coal tar coking inhibitor according to claim 1, wherein the solvent is one or more of benzene, toluene, xylene, trimethylbenzene, kerosene, light diesel oil and wash oil.
7. A preparation method of a coal tar coking inhibitor is characterized by comprising the following steps: 1) preparing materials according to a set mass percentage in advance;
2) adding a certain amount of solvent into a blending device according to a certain proportion, and starting a stirrer for stirring;
3) and sequentially adding solid raw materials in an antioxidant, a free radical deactivator, a metal surface passivator and an asphaltene dispersant, heating to a temperature T required by blending, adding liquid raw materials in the antioxidant, the free radical deactivator, the metal surface passivator and the asphaltene dispersant after uniform mixing, and cooling to below 35 ℃ after uniform mixing to obtain the coal tar coking inhibitor.
8. The method for preparing the coal tar coking inhibitor according to claim 7, wherein the temperature T is 45-180 ℃, and the stirring speed is 80-500 rpm.
9. The application of the coal tar coking inhibitor is characterized in that the coal tar coking inhibitor is added into a heating homogenizer with coal tar according to the proportion of 0.03-0.05 percent of the total weight of the coal tar.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112708491A (en) * | 2020-12-15 | 2021-04-27 | 湖北美和科技有限公司 | Coking inhibitor applied to biomass fuel furnace and preparation method thereof |
| CN112852189A (en) * | 2021-01-21 | 2021-05-28 | 山东联科科技股份有限公司 | Preparation method of carbon black |
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| CN101469280A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Coking and fouling inhibitor and use method thereof in heavy oil precessing system |
| CN101979471A (en) * | 2010-11-17 | 2011-02-23 | 湖南长岭石化科技开发有限公司 | Coal tar and crude benzene hydrogenated special coke inhibitor and preparation method thereof |
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Patent Citations (3)
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| CN101469280A (en) * | 2007-12-28 | 2009-07-01 | 中国石油化工股份有限公司 | Coking and fouling inhibitor and use method thereof in heavy oil precessing system |
| CN101250437A (en) * | 2008-03-28 | 2008-08-27 | 湖南长岭石化科技开发有限公司 | Coke inhibitor as well as preparation method and use thereof |
| CN101979471A (en) * | 2010-11-17 | 2011-02-23 | 湖南长岭石化科技开发有限公司 | Coal tar and crude benzene hydrogenated special coke inhibitor and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708491A (en) * | 2020-12-15 | 2021-04-27 | 湖北美和科技有限公司 | Coking inhibitor applied to biomass fuel furnace and preparation method thereof |
| CN112852189A (en) * | 2021-01-21 | 2021-05-28 | 山东联科科技股份有限公司 | Preparation method of carbon black |
| CN112852189B (en) * | 2021-01-21 | 2022-04-05 | 山东联科科技股份有限公司 | Preparation method of carbon black |
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