CN104357082B - A kind of for removing the composite deacidifying agent of aphthenic acids in diesel oil - Google Patents

A kind of for removing the composite deacidifying agent of aphthenic acids in diesel oil Download PDF

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Publication number
CN104357082B
CN104357082B CN201410602383.XA CN201410602383A CN104357082B CN 104357082 B CN104357082 B CN 104357082B CN 201410602383 A CN201410602383 A CN 201410602383A CN 104357082 B CN104357082 B CN 104357082B
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agent
deacidification
ratio
base
organic
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CN201410602383.XA
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CN104357082A (en
Inventor
钟读乐
于海斌
赵训志
曲晓龙
张永惠
石芳
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CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • 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
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203—Naphthenic acids, TAN
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention is a kind of for removing the composite deacidifying agent of aphthenic acids in diesel oil, is characterised by: with sodium hydroxide inorganic base for deacidification host, and organic base, inorganic salt and organic active agent are deacidification auxiliary agent；Wherein the content of inorganic base is 20～30%, and the content of organic base, inorganic salt and organic active agent is 2～10%, and surplus component is water；Wherein: described inorganic salt is one or both in potassium chloride, potassium sulfate, its ratio accounting for deacidification agent is 1～6%；Described organic base be ethanolamine, diethanolamine, triethanolamine one or more, ratio is 3～7%；Described organic active agent be anion surfactant, cationic surfactant, nonionic surfactant one or more, ratio is 1～2%；The alkali liquor that composite deacidifying agent can directly be replaced in refinery's diesel caustic washing technique under not changing process conditions produces, and addition is less, occurs without emulsion, and alkaline residue discharge capacity is little, and production cost is relatively low.

Description

A kind of for removing the composite deacidifying agent of aphthenic acids in diesel oil
Technical field
The present invention relates to PETROLEUM PROCESSING field, a kind of for removing the composite deacidifying of aphthenic acids in diesel oil Agent.
Background technology
At present, along with the exhaustion of world's crude resources and constantly bringing forth new ideas of production technique, the yield of high-acid crude oil with The increasing rate of annual 0.3%.High-acid crude oil processing during, acidic materials therein (predominantly ring Alkanoic acid) mainly have a strong impact on its normal course of processing and the serviceability of oil product.For that purpose it is necessary to by oil product In aphthenic acids remove to reach industrial requirements.At present, oil product deacidification is mainly from the standpoint of two: one is to destroy Property ground removing acid molecule in carboxyl (chemical method removing aphthenic acids), mainly have: alkali cleaning deacidification, alcohol ammonia process take off Acid, esterification deacidification, hydrogenation method, thermal decomposition method etc.；Two is the (thing that aphthenic acids overall separation recovery is used Logos removing aphthenic acids), mainly have: solvent extraction deacidification, adsorbing separation deacidification, membrance separation deacidification, microwave Radiation deacidification, electrically separated deacidification etc..In the diesel oil of current each refinery, the removing of aphthenic acids is basic uses traditional alkali Washing technique, but traditional alkali washing process emulsifying degree is big, alkali liquor discharge capacity is big, and environment causes bigger pollution. CN1740276A discloses the process removing aphthenic acids from diesel oil, and acid removal rate reaches 98%, and oil product returns Yield reaches 99%, emulsion does not occurs, but the method uses microwave radiation, and commercial production need to be to process units Improve, increase efficient microwave response system, it is seen that the method industrialization has bigger difficulty. CN10665716A discloses a kind of containing cyclohexylamine and the composite deacidifying agent of Organic Alcohol, has preferable deacidification Effect, and do not produce emulsifying, Organic Alcohol is recycled utilization, but relatively big owing to differing with current refinery processes, And there is not retracting device in major part refinery, it is seen that this composite deacidifying agent industrialization has certain difficulty.
The present invention is to improve alkali liquor on traditional alkali washing process, makes suitable composite deacidifying agent, Use this composite deacidifying agent can reduce emulsifying degree significantly, and on the premise of not increasing cost, reduce alkali The discharge of slag, thus reduce the impact on environment.
Summary of the invention
It is an object of the invention to be to provide a kind of composite deacidifying agent being applicable to diesel oil tradition alkali washing process, this is multiple The advantages such as it is few that conjunction deacidification agent has addition, emulsion, low cost does not occurs, and alkaline residue discharge capacity is few.
The present invention is a kind of for removing the composite deacidifying agent of aphthenic acids in diesel oil, it is characterised in that: composite deacidifying Agent is with sodium hydroxide inorganic base for deacidification host, and organic base, inorganic salt and organic active agent are deacidification auxiliary agent；Its The content of middle inorganic base is 20～30%, and the content of organic base, inorganic salt and organic active agent is 2～10%, Surplus component is water；Wherein inorganic base and organic base act primarily as the effect of removing aphthenic acids, inorganic salt and organic work Property agent acts primarily as the effect of breakdown of emulsion and Accelerated subsidence；
Wherein: described inorganic salt is one or both in potassium chloride, potassium sulfate, it accounts for the ratio of deacidification agent It is 1～6%；
Described organic base be ethanolamine, diethanolamine, triethanolamine one or more, it accounts for deacidification agent Ratio is 3～7%；
Described organic active agent is anion surfactant, cationic surfactant, non-ionic surface work One or more of property agent, the ratio wherein accounting for deacidification agent is 1～2%；
Composite deacidifying agent can directly replace the alkali liquor in refinery's diesel caustic washing technique under not changing process conditions Producing, and addition is less, occur without emulsion, alkaline residue discharge capacity is little, and production cost is relatively low.
It is embodied as example
In order to further illustrate the technical characteristic of the present invention, enumerate following example.
Embodiment 1
Using sodium hydroxide as host, it accounts for the 22% of deacidification agent ratio, and potassium chloride is auxiliary agent, and it accounts for deacidification agent Ratio is 4%, organic base be ethanolamine its account for the 3% of deacidification agent ratio, Organic substance be non-ionic surface live Property agent tween 80 its to account for deacidification agent ratio be 1%, surplus component is water；Each component is made into composite deacidifying agent 1.
Deacidification is tested: the acidity of raw oil is 34mgKOH/100ml, weighs after 1kg is heated to uniform temperature Adding 1g composite deacidifying agent, be sufficiently stirred for, stratification, obtain the limpid refined oil in upper strata, lower floor is Alkaline residue.
Breakdown of emulsion is tested: use raw oil and aphthenic acids to be configured to oil product that acid number is 20mgKOH/g is as former Material, weighs 50g high acid value oil product and adds in 100ml color comparison tube, be heated to uniform temperature, adds 5g and is combined Deacidification agent, shakes up reaction and observes emulsion.
Embodiment 2
Using sodium hydroxide as host, it accounts for the 27% of deacidification agent ratio, and potassium chloride is auxiliary agent, and it accounts for deacidification agent Ratio is 2%, organic base be diethanolamine its account for the 5% of deacidification agent ratio, Organic substance is cationic Activating agent quaternary ammonium salt its to account for deacidification agent ratio be 2%, surplus component is water；Each component is made into composite deacidifying Agent 2.
Deacidification experiment is carried out according in embodiment 1.Breakdown of emulsion experiment is carried out according in embodiment 1.
Embodiment 3
Using sodium hydroxide as host, it accounts for the 24% of deacidification agent ratio, and potassium chloride is auxiliary agent, and it accounts for deacidification agent Ratio is 3%, organic base be triethanolamine its account for the 4% of deacidification agent ratio, Organic substance be anionic surface live Property agent Sulfonates its to account for deacidification agent ratio be 1.5%, surplus component is water；Each component is made into composite deacidifying Agent 3.
Deacidification experiment is carried out according in embodiment 1.Breakdown of emulsion experiment is carried out according in embodiment 1.
Embodiment 4
Using sodium hydroxide as host, it accounts for the 26% of deacidification agent ratio, and potassium sulfate is auxiliary agent, and it accounts for deacidification agent Ratio is 3%, organic base be ethanolamine its account for the 4% of deacidification agent ratio, Organic substance be non-ionic surface live Property agent tween 80 its to account for deacidification agent ratio be 2%, surplus component is water；Each component is made into composite deacidifying agent 4.
Deacidification experiment is carried out according in embodiment 1.Breakdown of emulsion experiment is carried out according in embodiment 1.
Embodiment 5
Using sodium hydroxide as host, it accounts for the 25% of deacidification agent ratio, and potassium sulfate is auxiliary agent, and it accounts for deacidification agent Ratio is 4%, organic base be diethanolamine its account for the 5% of deacidification agent ratio, Organic substance is cationic Activating agent quaternary ammonium salt its to account for deacidification agent ratio be 2%, surplus component is water；Each component is made into composite deacidifying Agent 5.
Deacidification experiment is carried out according in embodiment 1.Breakdown of emulsion experiment is carried out according in embodiment 1.
Embodiment 6
Using sodium hydroxide as host, it accounts for the 26% of deacidification agent ratio, and potassium sulfate is auxiliary agent, and it accounts for deacidification agent Ratio is 2.5%, organic base be triethanolamine its account for the 3.5% of deacidification agent ratio, Organic substance is anionic surface Activating agent Sulfonates its to account for deacidification agent ratio be 2%, surplus component is water；Each component is made into composite deacidifying Agent 6.
Deacidification experiment is carried out according in embodiment 1.Breakdown of emulsion experiment is carried out according in embodiment 1.
Embodiment 7
Deacidification agent is certain industrial agent domestic, need to be diluted according to 1:8 during use.
Deacidification is tested: the acidity of raw oil is 34mgKOH/100ml, weighs after 1kg is heated to uniform temperature Adding 8g composite deacidifying agent, be sufficiently stirred for, stratification, obtain the limpid refined oil in upper strata, lower floor is Alkaline residue.
Breakdown of emulsion is tested: use raw oil and aphthenic acids to be configured to oil product that acid number is 20mgKOH/g is as former Material, weighs 50g high acid value oil product and adds in 100ml color comparison tube, be heated to uniform temperature, adds 20g and is combined Deacidification agent, shakes up reaction and observes emulsion.
Deacidification experiment effect and the demulsification of above 6 examples are as shown in the table.

Claims (1)

1. the composite deacidifying agent being applied in oil product remove aphthenic acids, it is characterised in that: composite deacidifying agent With sodium hydroxide inorganic base for deacidification host, organic base, inorganic salt and organic active agent are deacidification auxiliary agent；Wherein The content of inorganic base is 20～30%, and the content of organic base, inorganic salt and organic active agent is 2～10%, remaining Amount component is water；Wherein inorganic base and organic base play the effect of removing aphthenic acids, and inorganic salt and organic active agent rise Breakdown of emulsion and the effect of Accelerated subsidence；
Wherein: described inorganic salt is one or both in potassium chloride, potassium sulfate, it accounts for the ratio of deacidification agent It is 1～6%；
Described organic base be ethanolamine, diethanolamine, triethanolamine one or more, it accounts for deacidification agent Ratio is 3～7%；
Described organic active agent is anion surfactant, cationic surfactant, non-ionic surface work One or more of property agent, the ratio wherein accounting for deacidification agent is 1～2%；
Composite deacidifying agent can directly replace the alkali liquor in refinery's diesel caustic washing technique under not changing process conditions Producing, and addition is less, occur without emulsion, alkaline residue discharge capacity is little, and production cost is relatively low.
CN201410602383.XA 2014-10-31 2014-10-31 A kind of for removing the composite deacidifying agent of aphthenic acids in diesel oil Active CN104357082B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108504384A (en) * 2018-03-28 2018-09-07 陈太师 A kind of preparation method of diesel acid stripping agent

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105296005A (en) * 2015-10-14 2016-02-03 中国石油化工股份有限公司 Refined furfural deacidification agent and preparation method thereof
RO132925A3 (en) * 2018-06-12 2019-12-30 Igor Statnîi Multifunctional polymethylamine surface-active agent and process for preparing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1047882A (en) * 1990-07-27 1990-12-19 中国石油化工总公司武汉石油化工厂 Add the emulsification in the agent inhibition virgin oil alkaline cleaning procedure
CN1632068A (en) * 2004-11-26 2005-06-29 北京迪威尔石油天然气技术开发有限公司 Crude oil deacidification process
KR101241301B1 (en) * 2012-05-04 2013-03-11 주식회사 그린테크놀로지 Demusifier for oil field
CN103275753A (en) * 2013-05-31 2013-09-04 沈红新 Multifunctional crude oil tank farm treating agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1047882A (en) * 1990-07-27 1990-12-19 中国石油化工总公司武汉石油化工厂 Add the emulsification in the agent inhibition virgin oil alkaline cleaning procedure
CN1632068A (en) * 2004-11-26 2005-06-29 北京迪威尔石油天然气技术开发有限公司 Crude oil deacidification process
KR101241301B1 (en) * 2012-05-04 2013-03-11 주식회사 그린테크놀로지 Demusifier for oil field
CN103275753A (en) * 2013-05-31 2013-09-04 沈红新 Multifunctional crude oil tank farm treating agent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108504384A (en) * 2018-03-28 2018-09-07 陈太师 A kind of preparation method of diesel acid stripping agent
CN108504384B (en) * 2018-03-28 2020-09-08 福州专志信息技术有限公司 Preparation method of diesel deacidification agent

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