CN106590734B - A kind of method of shale diesel oil neutral and alkali nitride concentration and separation - Google Patents
A kind of method of shale diesel oil neutral and alkali nitride concentration and separation Download PDFInfo
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- CN106590734B CN106590734B CN201611132250.6A CN201611132250A CN106590734B CN 106590734 B CN106590734 B CN 106590734B CN 201611132250 A CN201611132250 A CN 201611132250A CN 106590734 B CN106590734 B CN 106590734B
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- diesel oil
- shale
- alkali
- concentration
- neutral
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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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
-
- 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
Abstract
The present invention relates to a kind of method of concentration and separation shale diesel oil neutral and alkali nitride, the core of this method is the separation method being combined using solvent refining and column chromatography.Extractant used is mixed into carry out solvent refining with shale oil diesel oil distillate in proportion, the tapped oil of preliminary concentration basic nitrogen compound is obtained after refined；The raw material that tapped oil is enriched with as basic nitrogen compound depth, then obtain basic nitrogen compound through the further concentrating and separating of column chromatography, desolventizing, vacuum drying.
Description
Technical field
The application belongs to shale oil processing technique field, and in particular to a kind of shale diesel oil neutral and alkali nitride concentration and separation
Method.
Background technology
Shale oil is the potential energy source of storage capacity very abundant in the world, its total storage capacity is considerably beyond oil.With day
Right oil is compared, and the non-hydrocarbon compounds such as substantial amounts of unsaturated hydrocarbons and N, S, O are contained in shale oil.In China, shale oil is most of
Extensive style burning is carried out as fuel, produces substantial amounts of NO in combustionxAnd SO2, energy profit while causing environmental pollution
It is low with being worth.Nitrogenate in oil product generally can be divided into basic nitrogen compound and non basic nitrogen compound.The presence of basic nitrogen compound
Reprocessing and utilization on shale oil have direct influence, are the noxious materials that remove or convert, but itself be very
Valuable industrial chemicals.Basic nitrogen compound is widely used in the fields such as industry, medicine, preservative, flotation agent, synthetic material.Closely
In the past few years, the research for basic nitrogen compound being extracted from coal tar, shale oil and oil product has caused the wide of domestic and international researcher
General concern.
At present, the extracting method of shale oil neutral and alkali nitride mainly has solvent refining, Separation by Complexation, soda acid elution, column
Combination of chromatography, thin-layer chromatography and the above method etc..
Solvent refining is a kind of new isolation technics developed rapidly in 20th century, i.e. solvent extraction, the method for use
For the similar principle that mixes, according to solubility of the basic nitrogen compound to be separated in oil product between the solvent of use difference
Selectively it is isolated, separating effect is preferable.
What Separation by Complexation method was applied is Lewis acid-base theories, complexing agent and basic nitrogen compound in Lewis acid and Lewis alkali
Complexing power under, form complex compound and oil phase and be layered, so that basic nitrogen compound be separated from oil product.But directly with complexing
Refinement treatment shale oil, then it is ineffective.103937522 A of Chinese patent CN disclose the separation of nitrogenous compound in coal tar
Method, the Separation by Complexation agent of use contain metal chloride, phosphate and halogeno salt, wherein metal chloride and halo salt quality
Than being 0.04~0.15 for the mass ratio of 0.05~0.2, phosphate and halogeno salt, the mass ratio of Separation by Complexation agent and coal tar is
0.05~0.7.The method achieve nitrogenous compound in coal tar, optionally quick separating, separating effect are preferable.But the party
Separation by Complexation agent cost is higher used by method, prepares more complicated.
Soda acid elution is according to the principle that basic nitrogen compound is reacted alkali with alkalescence using acid-base neutralization and strong acid
Property nitride separation comes out.United States Patent (USP) US 52637 is first to add a kind of opposite shale oil to have easily mixing compared with high volatile
Apolar diluent, or use direct-fired method, to reduce the viscosity of shale oil, then with it is a kind of by formic acid, acetic acid,
The selective solvents of one or more of compositions in trichloroacetic acid extract nitride, can be removed respectively with formic acid and acetic acid
76.38%th, 87.62% nitrogen.This method high selectivity, but soda acid need to be largely used, equipment anticorrosion is required high.
Column chromatography belongs to liquid-solid adsorption chromatography, it is a kind of technology of the principle based on absorption-dissolving.Using two-phase it
Between the various molecular separating force such as Van der Waals force and hydrogen bond effect, when mixture solution is added in stationary phase, each group in mixture
Divide and the surface of solids is attracted to different action intensities.Since adsorbent is different to the adsorption capacity of each material, adsorb strong
Component distributed in mobile phase it is few, and adsorb weak component distributed in mobile phase it is more so that each component in mixture obtains
Efficiently separate.
Thin-layer chromatography belongs to solid-liquid adsorption chromatography, is a kind of micro method for separating and analyzing, has that equipment is simple, speed
Hurry up, good separating effect, high sensitivity the advantages that, but be only applicable to the separation of low-volume samples.
The content of the invention
The present invention is directed to above-mentioned problems of the prior art, there is provided a kind of shale diesel oil neutral and alkali nitride enrichment
Separated method.The separation method that this method is combined using solvent refining and column chromatography, it is easy to operate feasible, can be by basic nitrogen
Compound is separated with hydro carbons, non basic nitrogen compound, phenolic compound, the basic nitrogen compound in shale oil is obtained effectively enrichment point
From.
Technical scheme comprises the following steps：
By extractant and shale diesel oil 0.3-2 in molar ratio：The mixing of 1 ratio is stirred reaction, during one section of standing sedimentation
Between after oil product be divided into two layers, the extractants of the upper and lower can be recycled by being evaporated under reduced pressure, and be recycled；After lower floor takes off extractant
Obtain the tapped oil of preliminary concentration basic nitrogen compound；Tapped oil is through column chromatography concentrating and separating, acid extracting alkali compounds, alkali neutralization
Acid, solvent back suction carry basic nitrogen compound, desolventizing, are dried in vacuo to obtain basic nitrogen compound.
The extractant for n,N-Dimethylformamide, furfural, dimethyl sulfoxide (DMSO), 1-methyl-2-pyrrolidinone one kind or
It is several.
The stirring reaction temperature is 50-80 DEG C.
The sedimentation time is 10-50min.
The column chromatography solid absorbent is silica gel.
The column chromatography mobile phase is petroleum ether, benzene/methanol mixed solution.
The volume ratio of benzene/methanol mixed solution is 1-2 in the column chromatography mobile phase：1.
The acid is hydrochloric acid, concentration 3mol/L.
The alkali is sodium hydroxide or potassium hydroxide.
The solvent is n-hexane.
Advantages of the present invention effect is as follows：
The separation method that the present invention is combined using solvent refining and column chromatography, it is easy to operate feasible, can be by alkali nitride
Thing is separated with hydro carbons, non basic nitrogen compound, phenolic compound, is conducive to the concentration and separation of basic nitrogen compound.Meanwhile both avoided
A large amount of acid, the use of aqueous alkali, extractant recoverable, greatly reduces production cost, and makes the alkalescence in shale oil
Nitride obtains effective concentration and separation, improves the comprehensive utilization value of shale oil, while is conducive to processing, being smart for shale oil
System.
Brief description of the drawings
Fig. 1 is the chromatogram of final product.
Embodiment
Embodiment 1
90ml n,N-Dimethylformamide is taken to mix (molar ratio 0.3 with 300ml shale diesel oils:1), heating water bath stirs
Mix, set heating-up temperature as 50 DEG C, after stirring, pour into separatory funnel and treat that sample is layered, after standing 10min, by lower floor
Oil product distilled, obtain tapped oil and n,N-Dimethylformamide, n,N-Dimethylformamide recycles.By tapped oil
Pillar layer separation is carried out, silica gel 50g is weighed, successively with 80mL petroleum ethers, 80mL benzene/methanol mixed solution (volume ratio 1：1)
Chromatographic elution is carried out to chromatographic column.Obtained benzene/methanol goes out liquid and isolates benzene layer solution after water extracts 3 times, then uses 3mol/
The HCl extracting benzene layer solution of L obtains inorganic layer, inorganic layer is carried out with the NaOH solution of 6mol/L to be neutralized to PH=11, afterwards
Add n-hexane to extract 3 times, basic nitrogen compound is extracted from water phase, solvent is steamed, obtains basic nitrogen compound.
Embodiment 2
By extractant dimethyl sulfoxide (DMSO) and shale diesel oil in molar ratio 0.5:The mixing of 1 ratio is stirred reaction, and stirring is anti-
It is 50 DEG C to answer temperature, and oil product is divided into two layers after standing sedimentation 20min, and the extractant of the upper and lower can be by being evaporated under reduced pressure back
Receive, recycle；Lower floor obtains the tapped oil of preliminary concentration basic nitrogen compound after taking off extractant；Tapped oil is through column chromatography concentration point
From, acid extracting alkali compounds, alkali neutralization acid, solvent back suction carry basic nitrogen compound, desolventizing, be dried in vacuo to obtain alkali nitride
Thing.The column chromatography solid absorbent is silica gel；The column chromatography mobile phase is petroleum ether, benzene/methanol mixed solution；
The volume ratio of benzene/methanol mixed solution is 1：1；Other steps are the same as embodiment 1.
Embodiment 3
By extractant 1-methyl-2-pyrrolidinone and shale diesel oil in molar ratio 1:The mixing of 1 ratio is stirred reaction, stirs
Reaction temperature is 70 DEG C, and oil product is divided into two layers after standing sedimentation 50min, and the extractant of the upper and lower can be by being evaporated under reduced pressure back
Receive, recycle；Lower floor obtains the tapped oil of preliminary concentration basic nitrogen compound after taking off extractant；Tapped oil is through column chromatography concentration point
From, acid extracting alkali compounds, alkali neutralization acid, solvent back suction carry basic nitrogen compound, desolventizing, be dried in vacuo to obtain alkali nitride
Thing.The column chromatography solid absorbent is silica gel；The column chromatography mobile phase is petroleum ether, benzene/methanol mixed solution；
The volume ratio of benzene/methanol mixed solution is 1.2：1；Other steps are the same as embodiment 1.
Embodiment 4
By extractant furfural and shale diesel oil in molar ratio 1:The mixing of 1 ratio is stirred reaction, and stirring reaction temperature is
60 DEG C, oil product is divided into two layers after standing sedimentation 30min, and the extractant of the upper and lower, which can pass through, is evaporated under reduced pressure recycling, circulation profit
With；Lower floor obtains the tapped oil of preliminary concentration basic nitrogen compound after taking off extractant；Tapped oil is extracted through column chromatography concentrating and separating, acid
Alkali compounds, alkali neutralization acid, solvent back suction carry basic nitrogen compound, desolventizing, are dried in vacuo to obtain basic nitrogen compound.The column
Chromatography solid adsorbent is silica gel；The column chromatography mobile phase is petroleum ether, benzene/methanol mixed solution；Benzene/methanol mixing is molten
The volume ratio of liquid is 1：1；Other steps are the same as embodiment 1.
Embodiment 5
By extractant n,N-Dimethylformamide and shale diesel oil in molar ratio 2:The mixing of 1 ratio is stirred reaction, stirs
It is 80 DEG C to mix reaction temperature, and oil product is divided into two layers after standing sedimentation 50min, and the extractant of the upper and lower can pass through vacuum distillation
Recycling, recycles；Lower floor obtains the tapped oil of preliminary concentration basic nitrogen compound after taking off extractant；Tapped oil is concentrated through column chromatography
Separation, acid extracting alkali compounds, alkali neutralization acid, solvent back suction carry basic nitrogen compound, desolventizing, are dried in vacuo to obtain alkali nitride
Thing.The column chromatography solid absorbent is silica gel；The column chromatography mobile phase is petroleum ether, benzene/methanol mixed solution；
The volume ratio of benzene/methanol mixed solution is 2：1；Other steps are the same as embodiment 1.
Result of implementation
The final product being enriched with by gas chromatograph-mass spectrometer (GC-MS) (GC-MS) to embodiment 4 characterizes, the result is shown in
Fig. 1 and table 1.The gradient enrichment of 4 neutral and alkali nitride of embodiment the results are shown in Table 2.
The method that basic nitrogen compound in shale oil can be combined by solvent refining and column chromatography is effectively enriched with
With separating, the mass fractions relative of basic nitrogen compound is by 12.08% gradient centrifugation of tapped oil to final enriched product
69.48%.60 kinds of basic nitrogen compounds are identified in the final product of concentration and separation, wherein predominantly aniline, pyridine, quinoline
The alkyl-substituted compounds such as quinoline, isoquinolin.
The GC-MS results of 1 final product of table
The gradient enrichment result of 2 shale diesel oil neutral and alkali nitride of table
Claims (10)
1. a kind of method of shale diesel oil neutral and alkali nitride concentration and separation, its feature：This method comprises the following steps：Will extraction
Agent is mixed in a certain ratio with shale oil diesel oil distillate, is stirred reaction at a certain temperature, standing sedimentation for a period of time after
Oil product is divided into two layers, and the extractant of the upper and lower can be recycled by being evaporated under reduced pressure, and be recycled, lower floor obtains after taking off extractant
The tapped oil of preliminary concentration basic nitrogen compound, tapped oil through column chromatography concentrating and separating, acid extracting alkali compounds, alkali neutralization acid,
Solvent back suction carries basic nitrogen compound, desolventizing, is dried in vacuo to obtain basic nitrogen compound.
A kind of 2. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1, it is characterised in that：Extraction
It is 0.3-2 to take the mass ratio of agent and shale diesel oil：1.
3. a kind of method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1 or 2, its feature exist
In：The extractant is n,N-Dimethylformamide, furfural, dimethyl sulfoxide (DMSO), the one or more of 1-methyl-2-pyrrolidinone.
A kind of 4. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1, it is characterised in that：Institute
The stirring reaction temperature stated is 50-80 DEG C.
A kind of 5. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1, it is characterised in that：It is heavy
The drop time is 10-50min.
A kind of 6. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1, it is characterised in that：Column
Chromatography solid adsorbent is silica gel, and mobile phase is both petroleum ether and benzene/methanol mixed solution.
A kind of 7. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 6, it is characterised in that：Column
The volume ratio of benzene/methanol mixed solution is 1-2 in chromatogram flow phase：1.
A kind of 8. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1, it is characterised in that：Institute
The acid stated is hydrochloric acid, concentration 3mol/L.
A kind of 9. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1, it is characterised in that：Institute
The alkali stated uses sodium hydroxide or potassium hydroxide.
A kind of 10. method of shale diesel oil neutral and alkali nitride concentration and separation according to claim 1, it is characterised in that：
The solvent is n-hexane.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960508A (en) * | 1989-01-30 | 1990-10-02 | Shell Oil Company | Two-step heterocyclic nitrogen extraction from petroleum oils |
| EP0538738A2 (en) * | 1991-10-15 | 1993-04-28 | General Sekiyu Kabushiki Kaisha | Desulfurization and Decolourizing of light oil by extraction |
| CN103396827A (en) * | 2013-07-31 | 2013-11-20 | 神华集团有限责任公司 | Separation method for alkali nitrogen compounds in coal liquefaction oil |
-
2016
- 2016-12-09 CN CN201611132250.6A patent/CN106590734B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4960508A (en) * | 1989-01-30 | 1990-10-02 | Shell Oil Company | Two-step heterocyclic nitrogen extraction from petroleum oils |
| EP0538738A2 (en) * | 1991-10-15 | 1993-04-28 | General Sekiyu Kabushiki Kaisha | Desulfurization and Decolourizing of light oil by extraction |
| CN103396827A (en) * | 2013-07-31 | 2013-11-20 | 神华集团有限责任公司 | Separation method for alkali nitrogen compounds in coal liquefaction oil |
Non-Patent Citations (4)
| Title |
|---|
| 我国页岩油非加氢脱氮技术的研究现状;刘洁等;《现代化工》;20150531;第35卷(第5期);第21-26页 * |
| 抚顺页岩油新型加工工艺研究;李广欣;《现代化工》;20110228;第31卷(第2期);第74-78页 * |
| 抚顺页岩油柴油馏分含氧、氮化合物类型研究;吴洪新等;《精细石油化工》;20150930;第32卷(第5期);第47-51页 * |
| 页岩油抽出油中氮化物的提取方法研究;李萍等;《石化技术与应用》;20110131;第29卷(第1期);第45-47页 * |
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