CN103396827B - The separation method of liquefied coal coil neutral and alkali nitrogen compound - Google Patents
The separation method of liquefied coal coil neutral and alkali nitrogen compound Download PDFInfo
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- CN103396827B CN103396827B CN201310329826.8A CN201310329826A CN103396827B CN 103396827 B CN103396827 B CN 103396827B CN 201310329826 A CN201310329826 A CN 201310329826A CN 103396827 B CN103396827 B CN 103396827B
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Abstract
The invention discloses a kind of separation method of liquefied coal coil neutral and alkali nitrogen compound.This separation method comprises the following steps: acid pickling step: mixed with acidic solution by liquefied coal coil and shake, stratification, is separated and obtains aqueous phase solution; Organic solvent extraction: the pH value of aqueous phase solution is adjusted to 8 ~ 10, adds organic solvent after cooling, mixes and shakes, stratification, is separated and obtains the organic phase solution being enriched with basic nitrogen compound.Apply the separation method of liquefied coal coil neutral and alkali nitrogen compound of the present invention, pickling is adopted to add organic solvent extractionprocess, basic nitrogen compound in liquefied coal coil is processed, reach that liquefied coal coil neutral and alkali nitrogen compound separation selectivity is good, resolution is high, extract effect thoroughly, and the organic phase solution obtained can be directly used in the analysis of basic nitrogen compound sample introduction.
Description
Technical field
The present invention relates to coal liquifaction coal chemical technology, especially relate to a kind of separation method of liquefied coal coil neutral and alkali nitrogen compound.
Background technology
Coal direct liquefaction as can a high effect cleaning coal technology of partial rcsponse China's oil resource supply and demand contradiction, have entered Commercial Demonstration operation stage at present.Containing a certain amount of nitrogenous compound in the thick product liquefied coal coil adopting direct coal liquefaction process to produce, wherein quite a few is basic nitrogen compound for this.And during liquefied coal coil further hydrofining production diesel oil fuel, basic nitrogen compound is one of principal element causing catalyst deactivation.For grasping catalyst deactivation mechanisms, need to do structural analysis to basic nitrogen compound component; Purify from liquefied coal coil and transform have high added value containing nitrogen compound to promote the economy of gelatin liquefaction technology further time, also need to do detailed analysis to the nitrogenous compound composition in liquefied coal coil.
But, liquefied coal coil component is except a certain amount of nitrogenous compound, also containing a large amount of hydrocarbons and sulfur-bearing, oxygenatedchemicals etc., for analyzing the basic nitrogen compound in liquefied coal coil as far as possible accurately, usually need to carry out pre-treatment to it, extract the basic nitrogen compound concentrated out in liquefaction oil, and then detailed proximate analysis is done to extract.But the separation method of liquefied coal coil neutral and alkali nitrogen compound of the prior art, there is basic nitrogen compound and be separated not exclusively, in extract, foreign matter content is many, causes the inaccurate problem of basic nitrogen compound composition analysis result.
Summary of the invention
The invention provides a kind of separation method of liquefied coal coil neutral and alkali nitrogen compound, be separated not exclusively to solve liquefied coal coil neutral and alkali nitrogen compound, in extract, foreign matter content is many, causes the inaccurate problem of basic nitrogen compound composition analysis result.
To achieve these goals, according to an aspect of the present invention, a kind of separation method of liquefied coal coil neutral and alkali nitrogen compound is provided.This separation method comprises the following steps: acid pickling step: mixed with acidic solution by liquefied coal coil and shake, stratification, is separated and obtains aqueous phase solution; Organic solvent extraction: the pH value of aqueous phase solution is adjusted to 8 ~ 10, adds organic solvent after cooling, mixes and shakes, stratification, is separated and obtains the organic phase solution being enriched with basic nitrogen compound.
Further, sulfuric acid or the hydrochloric acid of to be mass concentration the be 10wt% ~ 36wt% of the acidic solution in acid pickling step; The mass ratio of liquefied coal coil and acidic solution is 2:1 ~ 10:1.
Further, sulfuric acid or the hydrochloric acid of to be mass concentration the be 10wt% of the acidic solution in acid pickling step; The mass ratio of liquefied coal coil and acidic solution is 2:1 ~ 6:1.
Further, in acid pickling step, to mix and the time of shaking is 10 ~ 30 minutes, the time of stratification is 10 ~ 30 minutes.
Further, in organic solvent extraction by adding sodium hydroxide and/or the pH value of aqueous phase solution is adjusted to 8 ~ 10 by potassium hydroxide in aqueous phase solution.
Further, the organic solvent added in organic solvent extraction and the volume ratio of aqueous phase solution are 1:2 ~ 1:1.
Further, organic solvent is methylene dichloride.
Further, in organic solvent extraction, to mix and the time of shaking is 10 ~ 30 minutes, the time of stratification is 10 ~ 30 minutes.
Further, acid pickling step repeats 1 ~ 4 time, is merged by the aqueous phase solution collected, then carries out organic solvent extraction; Organic solvent extraction repeats 1 ~ 4 time, is merged by the organic phase solution collected, obtains the organic phase solution of enriched alkaline nitrogen compound.
Apply the separation method of liquefied coal coil neutral and alkali nitrogen compound of the present invention, pickling is adopted to add organic solvent extractionprocess, basic nitrogen compound in liquefied coal coil is processed, reach that liquefied coal coil neutral and alkali nitrogen compound separation selectivity is good, resolution is high, extract effect thoroughly, and the organic phase solution obtained can be directly used in the analysis of basic nitrogen compound sample introduction.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.The present invention is described in detail below in conjunction with embodiment.
Said in the present invention " liquefied coal coil " refers to that coal is under high-temperature and high-pressure conditions, the liquid fuel generated by catalytic hydrogenation and hydro-upgrading product thereof.
According to a kind of typical embodiment of the present invention, provide a kind of separation method of liquefied coal coil neutral and alkali nitrogen compound.This separation method comprises the following steps: acid pickling step: mixed with acidic solution by liquefied coal coil and shake, stratification, is separated and obtains aqueous phase solution; Organic solvent extraction: the pH value of aqueous phase solution is adjusted to 8 ~ 10, adds organic solvent after cooling, mixes and shakes, stratification, is separated and obtains the organic phase solution being enriched with basic nitrogen compound.
Because basic nitrogen compound has weakly alkaline, can react with acid and transfer to from liquefied coal coil in acidic solution, and hydrocarbons in liquefied coal coil can not react with acid and therefore adopts solution basic nitrogen compound selectivity in liquefied coal coil is good, resolution is high to be separated.
After also separation obtains aqueous phase solution at stratification, by adding excessive alkali in aqueous phase solution, pH value being adjusted to 8.0 ~ 10.0, neutralizing the acid in aqueous phase solution completely, again obtain weakly alkaline nitrogen compound; Because acid-base neutralisation can release certain heat, after aqueous phase is cooled to room temperature, then adds organic solvent and extract; Because basic nitrogen compound solubleness is in organic solvent larger, so can the basic nitrogen compound of the overwhelming majority be transferred in organic phase solution through extraction, stratification, isolates organic phase solution, can obtain the organic phase solution being enriched with basic nitrogen compound.The basic nitrogen compound being dissolved in organic solvent obtained like this direct injection can carry out subsequent analysis, and owing to eliminating impurity composition interference, the accuracy of analysis is high.
In acid pickling step, as long as the acidic solution used can react with basic nitrogen compound, basic nitrogen compound in gelatin liquefaction oil phase is transferred in aqueous phase, preferably, sulfuric acid or the hydrochloric acid of to be mass concentration the be 10wt% ~ 36wt% of the acidic solution in acid pickling step; The mass ratio of liquefied coal coil and acidic solution is 2:1 ~ 10:1; Further preferably, sulfuric acid or the hydrochloric acid of to be mass concentration the be 10wt% of the acidic solution in acid pickling step; The mass ratio of liquefied coal coil and acidic solution is 2:1 ~ 6:1, uses the acidic solution of this concentration range and mass ratio, can isolate the basic nitrogen compound in liquefied coal coil fully up hill and dale.
According to a kind of typical embodiment of the present invention, in acid pickling step, to mix and the time of shaking is 10 ~ 30 minutes, the time of stratification is 10 ~ 30 minutes.Such operating time design both can make aqueous phase fully contact with gelatin liquefaction oil phase and react, thus effectively isolated basic nitrogen compound, can reach higher working efficiency again.
In organic solvent extraction, aqueous phase solution pH value is adjusted to 8.0 ~ 10.0, namely the acid in aqueous phase solution is neutralized, again weakly alkaline nitrogen compound is obtained, preferably, by adding sodium hydroxide and/or the pH value of aqueous phase solution is adjusted to 8 ~ 10 by potassium hydroxide in aqueous phase solution in organic solvent extraction, sodium hydroxide and/or potassium hydroxide raw material are easy to get, and can not introduce impurity affect following component analysis.
As long as the volume ratio of the organic solvent added in organic solvent extraction and aqueous phase solution can make basic nitrogen compound, the solubleness in this organic solvent is obviously greater than the solubleness in aqueous phase, preferably, the organic solvent added in organic solvent extraction and the volume ratio of aqueous phase solution are 1:2 ~ 1:1.Preferably, this organic solvent is methylene dichloride, methylene dichloride can dissolve basic nitrogen compound in aqueous phase well and with aqueous phase layering well because density is greater than water, so decrease the loss in separatory process.Certainly, toluene is also passable, but toluene density is less than water, is in upper strata after layering, so loss is large in separatory process.
In organic solvent extraction, to mix and the time of shaking is 10 ~ 30 minutes, the time of stratification is 10 ~ 30 minutes, and such operating time design both can make organic solvent extraction process fully carry out, and can reach higher working efficiency again.
According to a kind of typical embodiment of the present invention, acid pickling step and organic solvent extraction all can according to actual needs repeatedly, under the prerequisite ensureing production efficiency and separating resulting, acid pickling step repeats 1 ~ 4 time, preferably, acid pickling step repeats 2 times, is merged by the aqueous phase solution collected, then carries out organic solvent extraction; Organic solvent extraction repeats 1 ~ 4 time, is merged by the organic phase solution collected, obtains the organic phase solution of enriched alkaline nitrogen compound.
Separation method of the present invention, being applicable in the concentration of basic nitrogen compound is apply in the liquefied coal coil of 0.01wt% ~ 2wt%, preferably, is apply in the liquefied coal coil of 0.1wt% ~ 2wt% in the concentration of basic nitrogen compound.Basic nitrogen lower than 0.01wt% content adopts this separation method, because concentration is too low, extracts error comparatively large, generally can not containing the basic nitrogen being greater than 2wt% content in liquefied coal coil product, and in principle higher than this content, this separation method is also out of question.
Usually, the subsequent component analysis that the phenolic compound being dissolved in organic solvent carries out is comprised: gas chromatographic analysis, Infrared spectroscopy, mass spectroscopy etc.
Below in conjunction with the embodiment of the present invention, be described in detail technical scheme of the present invention, but following embodiment is only understand the present invention, and can not limits the present invention, the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
Embodiment 1
Make solvent with toluene, be mixed with massfraction be 0.0296% pyridine, 0.0388% aniline, the quinoline of 0.0267%, the acridine of 0.0123% model compound (to simulate liquefied coal coil).
Get 30g model compound and be placed in separating funnel, the aqueous hydrochloric acid 5g adding 10% mass concentration shakes mixing 10 minutes, separate lower floor's aqueous phase after static 10 minutes, upper organic phase continues with the concussion mixing 10 minutes of the aqueous hydrochloric acid of identical amount and separates lower floor's aqueous phase after static 10 minutes; The aqueous phase collected adds the sodium hydroxide 12g of 10% mass concentration, the pH value of aqueous phase solution is adjusted to 8 ~ 10, add methylene dichloride after cooling to carry out extracting (volume ratio of methylene dichloride and aqueous phase is 1:2), each extraction time is 20 minutes, the lower floor's organic phase obtained is collected, air inlet analysis of hplc after quadruplication.The rate of recovery of the basic nitrogen compound (pyridine, aniline, quinoline, acridine) added is respectively 90.70%, 96.79%, 94.32%, 95.09%.
By the air inlet such as liquid and aqueous phase analysis of hplc more than after pickling, the basic nitrogen compound component of interpolation do not detected.
Embodiment 2
Identical with embodiment 1, make solvent with toluene, be mixed with massfraction be 0.0296% pyridine, 0.0388% aniline, the quinoline of 0.0267%, the acridine of 0.0123% model compound (to simulate liquefied coal coil).
Get 30g model compound and be placed in separating funnel, the aqueous hydrochloric acid 3g adding 36% mass concentration shakes mixing 30 minutes, separate lower floor's aqueous phase after static 30 minutes, upper organic phase continues with the concussion mixing 30 minutes of the aqueous hydrochloric acid of identical amount and separates lower floor's aqueous phase after static 30 minutes; The aqueous phase collected adds the sodium hydroxide 8g of 36% mass concentration, the pH value of aqueous phase solution is adjusted to 8 ~ 10, add methylene dichloride after cooling to carry out extracting (volume ratio of methylene dichloride and aqueous phase is 1:1), each extraction time is 20 minutes, the lower floor's organic phase obtained is collected, air inlet analysis of hplc after quadruplication.The rate of recovery of the basic nitrogen compound (pyridine, aniline, quinoline, acridine) added is respectively 91.35%, 94.27%, 95.38%, 94.19%.
By the air inlet such as liquid and aqueous phase analysis of hplc more than after pickling, the basic nitrogen compound component of interpolation do not detected.
Embodiment 3
With embodiment 1, with gelatin liquefaction petroleum naphtha unazotized after hydro-upgrading for solvent, be mixed with massfraction be 0.0443% pyridine, 0.0482% aniline, the quinoline of 0.0502%, the acridine of 0.0168% model compound.
Get 30g to add target upgrading petroleum naphtha and be placed in separating funnel, the aqueous sulfuric acid 5g adding 10% mass concentration shakes mixing 10 minutes, lower floor's aqueous phase is separated after static 10 minutes, the aqueous phase collected adds the potassium hydroxide 12g of 10% mass concentration, the pH value of aqueous phase solution is adjusted to 8 ~ 10, and the methylene dichloride adding 10 milliliters after cooling extracts, and extraction time is 20 minutes, collect the lower floor's organic phase obtained, air inlet analysis of hplc.
85.41%, 96.71%, 97.98%, 99.08% is respectively by the rate of recovery obtaining basic nitrogen compound (pyridine, aniline, quinoline, acridine) after pickling+extraction.
By the air inlet such as liquid and aqueous phase analysis of hplc more than after pickling, the basic nitrogen compound component of interpolation do not detected.
Embodiment 4
Separating step, with embodiment 1, after certain the gelatin liquefaction full distillate oil containing a certain amount of basic nitrogen compound being carried out the basic nitrogen compound that pickling+extraction extracts wherein, is done chromatogram/GC-MS analysis, 63 kinds of basic nitrogen compounds detected altogether; Liquid and aqueous phase etc. more than after pickling are carried out gas chromatographic analysis, substantially basic nitrogen compound do not detected.
Visible by embodiment 1-4, the present invention has this feature of weakly alkaline according to basic nitrogen compound, pickling is adopted to add organic solvent extractionprocess, liquefied coal coil is processed, the overall yield of basic nitrogen compound separation and Extraction reaches more than 94%, by mark-on reclaim calculate (quality that the quality of the basic nitrogen obtained after extraction mark-on liquefied coal coil deducts the basic nitrogen itself extracted in liquefied coal coil be namely extract add target basic nitrogen quality, with itself add target basic nitrogen quality and do recovery of standard addition than being namely this basic nitrogen) and residue model compound organic solution phase after pickling or gelatin liquefaction oil phase and the residue aqueous phase after extracting in the not separated basic nitrogen compound extracted all do not detected.As can be seen here, the present invention adopts pickling+organic solvent extraction to carry out the separation of liquefied coal coil neutral and alkali nitrogen compound, can basic nitrogen compound effectively in Extraction and separation liquefied coal coil, thorough to basic nitrogen compound, selectivity good, and separation efficiency is high, cost is low, the sample after process can direct injection analysis.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. a separation method for liquefied coal coil neutral and alkali nitrogen compound, is characterized in that, comprises the following steps:
Acid pickling step: mixed with acidic solution by described liquefied coal coil and shake, stratification, is separated and obtains aqueous phase solution;
Organic solvent extraction: the pH value of described aqueous phase solution is adjusted to 8 ~ 10, adds organic solvent after cooling, mixes and shakes, stratification, and be separated and obtain the organic phase solution being enriched with described basic nitrogen compound, described organic solvent is methylene dichloride;
In described acid pickling step, described mixing and concussion time be 10 ~ 30 minutes, the time of described stratification is 10 ~ 30 minutes; Sulfuric acid or the hydrochloric acid of to be mass concentration the be 10wt% of the described acidic solution in described acid pickling step; The mass ratio of described liquefied coal coil and described acidic solution is 2:1 ~ 6:1;
In described organic solvent extraction, described mixing and concussion time be 10 ~ 30 minutes, the time of described stratification is 10 ~ 30 minutes.
2. separation method according to claim 1, is characterized in that, by adding sodium hydroxide and/or the pH value of described aqueous phase solution is adjusted to 8 ~ 10 by potassium hydroxide in described aqueous phase solution in described organic solvent extraction.
3. separation method according to claim 1, is characterized in that, the described organic solvent added in described organic solvent extraction and the volume ratio of described aqueous phase solution are 1:2 ~ 1:1.
4. separation method according to any one of claim 1 to 3, is characterized in that,
Described acid pickling step repeats 1 ~ 4 time, is merged by the described aqueous phase solution collected, then carries out described organic solvent extraction;
Described organic solvent extraction repeats 1 ~ 4 time, is merged by the described organic phase solution collected, obtains the organic phase solution of basic nitrogen compound described in enrichment.
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| CN103923696B (en) * | 2014-04-29 | 2016-07-13 | 神华集团有限责任公司 | The separation method of aromatic hydrocarbon substance in aromatic hydrocarbon product and liquefied coal coil |
| CN106324158B (en) * | 2015-06-17 | 2018-11-16 | 中国石油天然气股份有限公司 | The method of nitrogenous compound in Solid Phase Extraction diesel oil |
| CN104927907B (en) * | 2015-07-01 | 2017-02-01 | 华东理工大学 | Alkylation product desulphurization and deacidifying method and device |
| CN106590734B (en) * | 2016-12-09 | 2018-05-04 | 辽宁石油化工大学 | A kind of method of shale diesel oil neutral and alkali nitride concentration and separation |
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| US20090120841A1 (en) * | 2007-11-14 | 2009-05-14 | Uop Llc, A Corporation Of The State Of Delaware | Methods of denitrogenating diesel fuel |
| CN102719267A (en) * | 2012-06-28 | 2012-10-10 | 神华集团有限责任公司 | Separation method for phenolic compound in coal liquefied oil |
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| US20090120841A1 (en) * | 2007-11-14 | 2009-05-14 | Uop Llc, A Corporation Of The State Of Delaware | Methods of denitrogenating diesel fuel |
| CN102719267A (en) * | 2012-06-28 | 2012-10-10 | 神华集团有限责任公司 | Separation method for phenolic compound in coal liquefied oil |
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