CN108441253A - A kind of antisludging agent for coker gasoline pipeline - Google Patents
A kind of antisludging agent for coker gasoline pipeline Download PDFInfo
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- CN108441253A CN108441253A CN201810065112.3A CN201810065112A CN108441253A CN 108441253 A CN108441253 A CN 108441253A CN 201810065112 A CN201810065112 A CN 201810065112A CN 108441253 A CN108441253 A CN 108441253A
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- Prior art keywords
- antisludging agent
- coker gasoline
- butyl
- pipeline
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Classifications
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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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
- C10G9/16—Preventing or removing incrustation
-
- 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
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of antisludging agents for coker gasoline pipeline.The group of the antisludging agent following masses percentage composition is grouped as：10 20% matal deactivator, 10 25% free radical terminators, 10 15% dispersants, 5 10w% scale removers, surplus are 200# solvent naphthas；Each component mass ratio is 20 30w% trihydroxyethyls mercaptans types, 25 35% octadecylamines, 35 55% dimercaptothiodiazoles wherein in matal deactivator；Free radical terminator is 40 50%2 sec-butyl, 46 dinitrophenol dinitrophenolate, 4 6%4 tert-butyl catechols, 44 56%N, N ' di-sec-butyl-p-phenyl enediamines；Dispersant is polyisobutene succinimide and benzotriazole, the Mannich derivative of benzaldehyde；Scale remover is the sulfurized alkylphenol calcium of 30w% dodecyl benzene sulfonic acid and 70w%400mgKOH/g.Antisludging agent of the present invention makes coker gasoline reduce fouling in pipeline by each component synergistic effect, extends the service life of equipment.Compared with the antisludging agent for being currently used for coker gasoline pipeline, strong applicability, scale-inhibiting properties are stablized.
Description
Technical field
The present invention relates to a kind of petroleum refining auxiliary agent fields, especially a kind of antisludging agent for coker gasoline pipeline.
Background technology
Delayed coking is one of important method of processing of heavy oil, and product coker gasoline can do second after hydrotreating
The raw material of alkene, catalytic reforming.But coker gasoline, in hydroprocessing processes, raw material filter, heat exchanger are susceptible to fouling, lead
Filter is caused frequently to unpick and wash, heat exchanger outlet temperature drops to not up to standard, and reactor pressure decrease rises very fast, seriously affects device
Normal operation.
By analyzing fouling sample in pipeline, and consults pertinent literature and learn that the mechanism of its fouling is：(1) coking
Unsaturated compound in gasoline is extremely unstable, the alkadienes especially contained, is easy polymerization and forms macromolecular organic compound
Object.(2) tiny coke powder is contained in coker gasoline, which is easily bonded together to form burnt dirt with macromolecular organic compound.⑶
The metal of equipment surface and the nickel in raw material are easily catalyzed by high temperature position occurs dehydrogenation reaction, promotes the formation of burnt dirt.(4) burnt
Changing the hetero atoms such as sulphur, the nitrogen in gasoline, easily decomposition generates free radicals at high temperature, causes radical reaction and forms high molecular polymerization
Object is further condensed coking.According to fouling mechanisms, domestic and international researcher has developed many plus hydrogen antisludging agent.
CN101265418B discloses a kind of antisludging agent of hydrogenation plant, by by alkyl salicylate and organic amine according to 1:1 carries out
Reaction obtains antisludging agent.CN107177378A discloses a kind of plus hydrogen antisludging agent, including the detersive of 10-30%, 5-10%
Antioxidant, the passivator of 0.5-2%, the antirust agent of 0.5-2%, the cosolvent of 1-2%, 50-70% organic solvent.At present
Market antisludging agent component function is single, and general applicability is not strong, leads to the problem of appearance effect differs in use.
Invention content
The technical problem to be solved by the present invention is to overcome the problems, such as that existing antisludging agent exists, according to the fouling of coker gasoline
Feature provides a kind of antisludging agent for coker gasoline pipeline.
A kind of antisludging agent for coker gasoline pipeline of the invention, is grouped as by the group of following mass percentage：10-
20% matal deactivator, 10-25% free radical terminators, 10-15% dispersants, 5-10% scale removers, surplus are that 200# is molten
Agent oil；
Each component mass ratio is 20-30% trihydroxyethyls mercaptans type, 25-35% octadecyls wherein in matal deactivator
Amine, 35-55% dimercaptothiodiazoles；
Free radical terminator be 40-50w%2- sec-butyl -4-6- dinitrophenol dinitrophenolates, 4-6w%4- tert-butyl catechols,
44-56w%N, N '-di-sec-butyl-p-phenyl enediamine；Dispersant is polyisobutene succinimide and benzotriazole, benzaldehyde
Mannich derivative；Scale remover is the sulfurized alkylphenol calcium of 30w% dodecyl benzene sulfonic acid and 70w%400mgKOH/g.
The preferred preparation method of dispersant in the Hydrogenation of Coker Gasoline antisludging agent is：Using dimethylbenzene as solvent,
Polyisobutene succinimide and benzotriazole are added, is heated to 75-80 DEG C, 110-120 DEG C is warming up to benzaldehyde is added
Being stirred makes it carry out Mannich reaction, and the filtering of 4-5h postcoolings, vacuum distillation obtain dispersant.
The present invention also provides a kind of applications of the antisludging agent for coker gasoline pipeline, by the antisludging agent in coking
It is injected at the coker gasoline outlet line of fractionating column, and the additive amount of antisludging agent is 100-200 μ g/g.
The present invention starts with for the antisludging agent of coker gasoline pipeline from mechanism carries out scale inhibition from the following aspects respectively：⑴
Matal deactivator is added, by being passivated to the catalytic action of the metal ions such as nickel, iron, dehydrogenative condensation reaction occurs for prevention,
Subtract the generation of burnt dirty predecessor.High-temperature corrosion inhibitor can form protective film in tube wall, slow down equipment corrosion.(2) free radical terminator is adopted
It is formed with antioxidant and polymerization inhibitor, terminates the progress of oxidation reaction respectively, block free chain reaction, prevent and reduce big point
The formation of sub- organic polymer.(3), using heat safe Mannich derivative as dispersant, short grained coke powder is divided
It dissipates, prevents its aggregation, be deposited on equipment surface.(4), using surfactant as scale remover, established burnt dirt is carried out molten
Solution, extends the service life of equipment.By above four aspects, the synergistic effect of nine kinds of substances makes coker gasoline subtract in pipeline
Few fouling, extends the service life of equipment.Simple with composition currently on the market, the antisludging agent having a single function is compared, and is had and is applicable in
Property it is strong, scale-inhibiting properties stablize.
Specific implementation mode
The antisludging agent technical solution for coker gasoline pipeline is further illustrated the present invention with reference to specific embodiment.
Embodiment 1
It is prepared by Mannich derivative：Using dimethylbenzene as solvent, the molar ratio of reactant is：Polyisobutene succinyl is sub-
Amine：Three nitrogen of benzo：Benzaldehyde=1:1:1.The circle containing dimethylbenzene is added in polyisobutene succinimide and benzotriazole
In the flask of bottom, 77 DEG C are heated to, the benzaldehyde added, which is warming up to 115 DEG C and is stirred, makes it carry out Mannich reaction, reaction
The filtering of 5h postcoolings, vacuum distillation obtain.
It takes 40g200# solvent naphthas to be heated to 70 DEG C and 5g trihydroxyethyls mercaptans type, 5g octadecylamines, 10g dimercaptos is added
Thiadiazoles stirring and dissolving adds 8g2- sec-butyl -4-6- dinitrophenol dinitrophenolates, 1g4- tert-butyl catechols, 11gN, N '-di-secondary
Butyl p-phenylenediamine stirring and dissolving adds 12g Mannich derivative 2.4g dodecyl benzene sulfonic acid and 5.6g400mgKOH/g
Sulfurized alkylphenol calcium constant temperature stir to dissolving, cooling obtains Hydrogenation of Coker Gasoline antisludging agent 1.
Embodiment 2
Man Nixi derivatives are prepared according to the preparation method of embodiment 1.
It takes 40g200# solvent naphthas to be heated to 70 DEG C and 4g trihydroxyethyls mercaptans type, 6g octadecylamines, 10g dimercaptos is added
Thiadiazoles stirring and dissolving adds 9g2- sec-butyl -4-6- dinitrophenol dinitrophenolates, 1.5g4- tert-butyl catechols, 9.5gN, N '-two
Secondary-butyl-p-phenylenediamine stirring and dissolving adds 13g Mannich derivative 2g dodecyl benzene sulfonic acid and 5g400mgKOH/g
Sulfurized alkylphenol calcium constant temperature is stirred to dissolving, and cooling obtains Hydrogenation of Coker Gasoline antisludging agent 2.
Embodiment 3
It is prepared by Mannich derivative：Using dimethylbenzene as solvent, the molar ratio of reactant is：Polyisobutene succinyl is sub-
Amine：Three nitrogen of benzo：Benzaldehyde=2:2:1.The circle containing dimethylbenzene is added in polyisobutene succinimide and benzotriazole
In the flask of bottom, 75 DEG C are heated to, the benzaldehyde added, which is warming up to 120 DEG C and is stirred, makes it carry out Mannich reaction, reaction
The filtering of 4.5h postcoolings, vacuum distillation obtain.
It takes 40g200# solvent naphthas to be heated to 70 DEG C and 5g trihydroxyethyls mercaptans type, 4g octadecylamines, 11g dimercaptos is added
Thiadiazoles stirring and dissolving adds 8.5g2- sec-butyl -4-6- dinitrophenol dinitrophenolates, 1g4- tert-butyl catechols, 10.5gN, N ' -
Di-sec-butyl-p-phenyl enediamine's stirring and dissolving, add 12.5g Mannich derivative 2g dodecyl benzene sulfonic acid and
The sulfurized alkylphenol calcium constant temperature of 5.5g400mgKOH/g is stirred to dissolving, and cooling obtains Hydrogenation of Coker Gasoline antisludging agent 3.
Embodiment 4
By above-mentioned three kinds plus hydrogen antisludging agent according to 100 μ g/g, 150 μ g/g, 200 ratios of μ g/g tri- are added to coker gasoline
In, stirring is obtained to being uniformly mixed containing the sample for adding hydrogen antisludging agent.
Embodiment 5
Add the evaluation method of hydrogen antisludging agent：
(1) the colloid of coker gasoline changes in simulation heating pipeline.It will be containing adding the oil product of hydrogen antisludging agent to be put into reaction under high pressure
Lead to nitrogen in kettle, after sealing into line replacement, be heated to 300 DEG C, constant temperature is kept for 4 hours, is taken out oil product and is carried out gum test.It measures
The results are shown in table below.
The colloid variation of the different adding proportions of table 1
| Number | 100μg/g | 150μg/g | 200μg/g |
| Blank sample | 32 | 31 | 33 |
| Embodiment 1 | 7 | 6 | 7 |
| Embodiment 2 | 8 | 7 | 6 |
| Embodiment 3 | 6 | 5 | 5 |
(2) iron plate method measures scale inhibition performance.After the iron plate of 3cm × 3cm × 0.2cm is carried out pickling processes, it is anti-to hang on high pressure
It answers in kettle, certain mass is added contains the oil product for adding hydrogen antisludging agent, it is ensured that iron plate is totally immersed into oil product, and nitrogen is led to after sealing
Into line replacement, 300 DEG C are heated to, constant temperature is kept for 4 hours, and taking-up iron plate dries after being rinsed well with dimethylbenzene and carries out quality survey again
It is fixed, calculate scale inhibition performance.
Iron plate quality before iron plate quality-experiment after burnt dirt quality=experiment
Scale inhibition performance=(the burnt dirty quality of the dirty quality-experiment of blank coke)/blank coke dirt quality * 100%
It is measured after the test, specific measurement result is as shown in the table.
The scale inhibition performance of the different adding proportions of table 2
| Number | 100μg/g | 150μg/g | 200μg/g |
| Embodiment 1 | 89.5% | 90.8% | 90.6% |
| Embodiment 2 | 88.9% | 89.3% | 90.4% |
| Embodiment 3 | 90.5% | 91.5% | 91.0% |
Claims (3)
1. a kind of antisludging agent for coker gasoline pipeline, which is characterized in that be grouped as by the group of following masses percentage composition：
The matal deactivator of 10-20%, 10-25% free radical terminators, 10-15% dispersants, 5-10% scale removers, surplus 200#
0 solvent naphtha；
Wherein in matal deactivator each component mass ratio be 20-30% trihydroxyethyls mercaptans type, 25-35% octadecylamines,
35-55% dimercaptothiodiazoles；
Free radical terminator is 40-50w%2- sec-butyl -4-6- dinitrophenol dinitrophenolates, 4-6w%4- tert-butyl catechols, 44-
56w%N, N '-di-sec-butyl-p-phenyl enediamine；
Dispersant is polyisobutene succinimide and benzotriazole, the Mannich derivative of benzaldehyde；
Scale remover is the sulfurized alkylphenol calcium of 30w% dodecyl benzene sulfonic acid and 70w%400mgKOH/g.
2. according to the antisludging agent described in claim 1, which is characterized in that the preparation method of the dispersant is：By diformazan
Benzene adds polyisobutene succinimide and benzotriazole, is heated to 75-80 DEG C as solvent, adds benzaldehyde heating
Being stirred to 110-120 DEG C makes it carry out Mannich reaction, is made after the filtering of 4-5h postcoolings, vacuum distillation.
3. a kind of application of antisludging agent for coker gasoline pipeline, which is characterized in that the antisludging agent is in coking fractional distillation column
Coker gasoline outlet line at inject, the additive amount of antisludging agent is 100-200 μ g/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065112.3A CN108441253A (en) | 2018-01-23 | 2018-01-23 | A kind of antisludging agent for coker gasoline pipeline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810065112.3A CN108441253A (en) | 2018-01-23 | 2018-01-23 | A kind of antisludging agent for coker gasoline pipeline |
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| CN108441253A true CN108441253A (en) | 2018-08-24 |
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| CN201810065112.3A Pending CN108441253A (en) | 2018-01-23 | 2018-01-23 | A kind of antisludging agent for coker gasoline pipeline |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678261A (en) * | 2019-02-01 | 2019-04-26 | 北京乐文科技发展有限公司 | One kind plus hydrogen anti-incrustation corrosion inhibitor and preparation method thereof |
| CN111925825A (en) * | 2020-07-28 | 2020-11-13 | 广东粤首新科技有限公司 | Scale inhibition and dispersion agent and preparation method and application thereof |
| CN117448037A (en) * | 2023-10-31 | 2024-01-26 | 山东澳润化工科技有限公司 | Scale inhibitor for high-temperature oil refining system and preparation method and application thereof |
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2018
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109678261A (en) * | 2019-02-01 | 2019-04-26 | 北京乐文科技发展有限公司 | One kind plus hydrogen anti-incrustation corrosion inhibitor and preparation method thereof |
| CN111925825A (en) * | 2020-07-28 | 2020-11-13 | 广东粤首新科技有限公司 | Scale inhibition and dispersion agent and preparation method and application thereof |
| CN117448037A (en) * | 2023-10-31 | 2024-01-26 | 山东澳润化工科技有限公司 | Scale inhibitor for high-temperature oil refining system and preparation method and application thereof |
| CN117448037B (en) * | 2023-10-31 | 2024-04-02 | 山东澳润化工科技有限公司 | Scale inhibitor for high-temperature oil refining system and preparation method and application thereof |
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Application publication date: 20180824 |