CN106675619A - Method for removing nitride in diesel fraction of shale oil by quaterisation reaction - Google Patents
Method for removing nitride in diesel fraction of shale oil by quaterisation reaction Download PDFInfo
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- CN106675619A CN106675619A CN201610568228.XA CN201610568228A CN106675619A CN 106675619 A CN106675619 A CN 106675619A CN 201610568228 A CN201610568228 A CN 201610568228A CN 106675619 A CN106675619 A CN 106675619A
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- Prior art keywords
- diesel oil
- reaction
- quaterisation
- shale oil
- oil distillate
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/26—Halogenated hydrocarbons
-
- 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
-
- 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 invention relates to a method for removing nitride in a diesel fraction of shale oil by quaterisation reaction. According to the method, halogenated hydrocarbon and a diesel fraction of shale oil are mixed in proportion to carry out a quaterisation reaction; after the reaction, precipitates are separated; a reagent in oils can be recovered and reused, and total nitrogen removal rate of the reaction reaches 30%; in addition, precipitates react with a precipitating agent to synthesize an ionic liquid for further utilization.
Description
Technical field
The present invention relates to nitrogenize in oil denitrification field, more particularly to a kind of quaterisation removing shale oil diesel oil distillate
The method of thing.
Background technology
Shale oil is a kind of important unconventional energy resource, main composition similar to natural oil, rich reserves, but its institute
The content of the miscellaneous element for containing is far above natural oil.Shale oil diesel oil distillate accounts for 46% or so, therefore the exploitation of its denitrification process is just
Progressively deeply.At present, denitrogenation method mainly has hydrodenitrogeneration technology and Non-hydrogenation technology technology, and Non-hydrogenation technology technology includes acid
Alkali refining method, solvent process, Complex denitrogenation technology, bio-denitrification technology etc..
Hydrodenitrogeneration technology actually reacts the nitrogen-containing compound in oil product with hydrogen in the presence of catalyst
The ammonia being easily removed is changed into, so as to the nitrogen-containing compound in oil product be taken off.But Hydrofining Technology equipment investment is higher, and
Its operating condition is more harsh, is not suitable for middle-size and small-size refinery.
Acid-alkali refining method is that colloid, asphalitine in the effect using concentrated sulphuric acid, with oil product etc. occur sulfonating reaction, so as to
Imurity-removal.Concentrated sulphuric acid concentration requirement more than 98%, it is noted that stirring during addition.Be except desulfonate after it is miscellaneous
The acid of matter and neutralization residual, adds sodium hydroxide to carry out alkali cleaning, to the aobvious neutrality of oil product.Final step is washed, and is washed off water-soluble
Property impurity.The method is more serious to equipment corrosion with simple to operate but dangerous larger, and the acid sludge after washing is difficult to process, right
The pollution that environment is caused is larger.
Solvent process is a kind of isolation technics got up in eighties of last century fast development, and the method for adopting mixes for similar
Principle, according to nitrogen-containing compound to be separated in oil product with adopt solvent between dissolubility difference selectively will
Its removing.CN 1197834A disclose the process that a kind of catalytic diesel oil extracts denitrification refining, it is characterized by selecting a kind of sulfur-bearing
Polar solvent and hydrogen bonds compound catalytic diesel oil is carried out as the two component composite extractants that additive is constituted it is multistage
Counter-current extraction, nitrogenous and sulfur-bearing the compound impurities in catalytic diesel oil etc. extract in composite extractant, the catalysis bavin after extraction
Oil obtains after washing refined diesel oil product.Impurity after extraction equally exists the problem for processing, and has greater environmental impacts.
Complexometry denitrogenation application is Lewis acid-base theories.By the stronger of the generation of Lewis acid and Lewis between sour
Mating reaction, make chelating agent react with basic nitrogen compound, complex is formed, so as to by the organonitrogen removal in oil product.
The A of CN 103666537 disclose a kind of wax tailings Complex denitrogenation process for purification, are made up of the component of following mass fractions：Network
Mixture 50% ~ 85%, precipitant 2% ~ 10%, corrosion inhibiter 0.5% ~ 10%, cosolvent 2% ~ 30%.Present invention ensure that Complex denitrogenation is refined
The high efficient and reliable of operation, can effectively remove various undesirable components in wax tailings, be avoided that again during complexation technique not
Corrosion is caused to equipment, while product rapid subsidence from oil product can be caused to separate.But the method is to process units
There is certain impact with environment, and the chelating agent reclaims more difficult, unsuitable secondary utilization.
Bio-denitrification technology is in recent years emerging denitrogenation technology, is mainly used in the aspects such as wastewater treatment.CN 105462902
A discloses a kind of biological amassing capacity of petroleum sweetening denitrogenation.It is using the hot glucoside ground bacillus w-1 after activation
Dwell thermobacillus, small-sized thermophilic acidophilic beam hanger bacterium by volume 1 with mycobacterium goodiii, new Apollo:1:1:1 composition.Mix micro- life
Thing microbial inoculum is reacted with high sulfur-containing diesel and slurry oil inferior respectively in inorganic salt solution, determines containing for reaction both front and back oil product
Sulfur, nitrogen content.But generally containing the element to such as harmful microorganism, such as arsenic, hydrargyrum, lead in oil.Therefore, the key of the method
It is how to turn out the denitrification microorganism resistant to poisonous substance, and reduces harm of the poisonous substance to microorganism, and is unfavorable for big
Technical scaleization is gone into operation.
In addition, though simple ionic liquid denitrogenation application denitrification percent is higher, ionic liquid cost costly, and synthesizes
Process is complex, is suitable only for laboratory research.
The content of the invention
The present invention is directed to above-mentioned problems of the prior art, there is provided a kind of quaterisation removes shale oil diesel oil
The method of nitride in fraction；The problem that denitrification process brings impurity treatment is overcome, and the present invention is except reaching denitrogenation
Purpose outside, also synthesized corresponding ionic liquid.
Technical scheme is comprised the following steps：
By halogenated alkane and shale oil diesel oil distillate in molar ratio (0.5-1):The mixing of 1 ratio carries out stirring reaction, oil after reaction
Product are divided into two-layer, obtain upper strata and the lower floor comprising the nitride composition taken off that solvent mixes with diesel oil distillate；Upper strata it is molten
Agent is reclaimed by vacuum distillation, is recycled, while the diesel oil distillate after being taken off；Lower floor's material such as is dissolved at the acetone of quality
In, continuing and the further stirring reaction of precipitant, precipitant is 1 with the mass ratio of lower floor's material：1, distill back after the completion of reaction
Acetone is received, weak yellow liquid is obtained.
Described stirring reaction temperature is 50-75 DEG C.
Described halogenated alkane includes bromoethane or halo normal butane.
Described precipitant is Sodium fluoroborate pressed powder.
Advantages of the present invention effect is as follows：
The inventive method by means of ionic liquid reaction mechanism process, bring impurity treatment etc. to ask while overcoming denitrification process
Topic, and synthesize ionic liquid after the reaction, it is easy to follow-up research and utilization；The inventive method is except reaching the purpose of denitrogenation
Outward, also and into corresponding ionic liquid, not only economic but also environmental protection, reagent is repeatable utilizes and environmentally safe.
Specific embodiment
Embodiment 1：
Take 100ml shale oil diesel oil distillate to mix with 50ml halogenated alkanes, heating in water bath stirring sets heating-up temperature as 50 DEG C,
Mixing time is 11h, after stirring terminates, pours in separatory funnel and treats that sample is layered, and the oil product on upper strata is distilled, and reclaims it
In halogenated alkane, measure its total nitrogen content；Lower floor is poured in conical flask, takes the Sodium fluoroborate powder of Isodose, and is added
50ml acetone is dissolved, and proceeds stirring reaction, and after band reaction terminates, Distillation recovery acetone obtains faint yellow viscous solution
Body；Total nitrogen removal efficiency is reacted up to 30%.
Described halogenated alkane is bromoethane.
Embodiment 2：
Take 100ml shale oil diesel oil distillate to mix with 50ml halogenated alkanes, heating in water bath stirring sets heating-up temperature as 65 DEG C,
Mixing time is 11h, after stirring terminates, pours in separatory funnel and treats that sample is layered, and the oil product on upper strata is distilled, and reclaims it
In halogenated alkane, measure its total nitrogen content；Lower floor is poured in conical flask, takes the Sodium fluoroborate powder of Isodose, and is added
50ml acetone is dissolved, and proceeds stirring reaction, and after band reaction terminates, Distillation recovery acetone obtains faint yellow viscous solution
Body；Total nitrogen removal efficiency is reacted up to 30%.
Described halogenated alkane is bromoethane.
Embodiment 3：Take 100ml shale oil diesel oil distillate to mix with 50ml halogenated alkanes, heating in water bath stirring, setting heating
Temperature is 65 DEG C, and mixing time is 11h, after stirring terminates, pours in separatory funnel and treats that sample is layered, and the oil product on upper strata is carried out
Distillation, reclaims halogenated alkane therein, measures its total nitrogen content；Lower floor is poured in conical flask, takes the Sodium fluoroborate of Isodose
Powder, and add 50ml acetone to be dissolved, proceeding stirring reaction, after band reaction terminates, Distillation recovery acetone obtains light
Yellow viscous liquid；Total nitrogen removal efficiency is reacted up to 30%.
Described halogenated alkane is halo normal butane.
Embodiment 4
Take 100ml shale oil diesel oil distillate to mix with 100ml halogenated alkanes, heating in water bath stirring sets heating-up temperature as 75 DEG C,
Mixing time is 11h, after stirring terminates, pours in separatory funnel and treats that sample is layered, and the oil product on upper strata is distilled, and reclaims it
In halogenated alkane, measure its total nitrogen content；Lower floor is poured in conical flask, takes the Sodium fluoroborate powder of Isodose, is dissolved in
In the acetone of the quality such as lower floor material, proceed stirring reaction, after band reaction terminates, Distillation recovery acetone obtains yellowish
Color thick liquid；Total nitrogen removal efficiency is reacted up to 30%.
Described halogenated alkane is bromoethane.
Claims (4)
1. the method that quaterisation removes nitride in shale oil diesel oil distillate, it is characterised in that comprise the steps：
By halogenated alkane and shale oil diesel oil distillate in molar ratio (0.5-1):The mixing of 1 ratio carries out stirring reaction, oil after reaction
Product are divided into two-layer, obtain upper strata and the lower floor comprising the nitride composition taken off that solvent mixes with diesel oil distillate；Upper strata it is molten
Agent is reclaimed by vacuum distillation, is recycled, while the diesel oil distillate after being taken off；Lower floor's material such as is dissolved at the acetone of quality
In, continuing and the further stirring reaction of precipitant, precipitant is 1 with the mass ratio of lower floor's material：1, distill back after the completion of reaction
Acetone is received, weak yellow liquid is obtained.
2. the method that quaterisation according to claim 1 removes nitride in shale oil diesel oil distillate, its feature exists
In described stirring reaction temperature be 50-75 DEG C.
3. the method that quaterisation according to claim 1 removes nitride in shale oil diesel oil distillate, its feature exists
Include bromoethane or halo normal butane in described halogenated alkane.
4. the method that quaterisation according to claim 1 removes nitride in shale oil diesel oil distillate, its feature exists
In described precipitant be Sodium fluoroborate pressed powder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610568228.XA CN106675619B (en) | 2016-07-19 | 2016-07-19 | The method that quaternization reaction removes nitride in shale oil diesel oil distillate |
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| CN201610568228.XA CN106675619B (en) | 2016-07-19 | 2016-07-19 | The method that quaternization reaction removes nitride in shale oil diesel oil distillate |
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| CN106675619A true CN106675619A (en) | 2017-05-17 |
| CN106675619B CN106675619B (en) | 2018-12-07 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881455A (en) * | 2021-10-26 | 2022-01-04 | 武汉工程大学 | Method for performing complex extraction denitrification and deslagging on waste oil distillation product oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225160A (en) * | 2008-02-21 | 2008-07-23 | 河南科技大学 | Method for preparing epoxy propyl ionic liquid and polyether-type macroion liquid |
| CN101967389A (en) * | 2010-10-27 | 2011-02-09 | 大庆油田有限责任公司 | Denitrifying agent for directly removing basic nitrogen compound from shale oil |
| CN102220162A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for reducing corrosivity of crude oil |
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- 2016-07-19 CN CN201610568228.XA patent/CN106675619B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101225160A (en) * | 2008-02-21 | 2008-07-23 | 河南科技大学 | Method for preparing epoxy propyl ionic liquid and polyether-type macroion liquid |
| CN102220162A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for reducing corrosivity of crude oil |
| CN101967389A (en) * | 2010-10-27 | 2011-02-09 | 大庆油田有限责任公司 | Denitrifying agent for directly removing basic nitrogen compound from shale oil |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113881455A (en) * | 2021-10-26 | 2022-01-04 | 武汉工程大学 | Method for performing complex extraction denitrification and deslagging on waste oil distillation product oil |
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