CN106542974A - A kind of method of sulfide in enrichment methyl tertiary-butyl ether - Google Patents
A kind of method of sulfide in enrichment methyl tertiary-butyl ether Download PDFInfo
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- CN106542974A CN106542974A CN201510595653.3A CN201510595653A CN106542974A CN 106542974 A CN106542974 A CN 106542974A CN 201510595653 A CN201510595653 A CN 201510595653A CN 106542974 A CN106542974 A CN 106542974A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
Abstract
The present invention relates in a kind of enrichment methyl tertiary-butyl ether sulfide method, enrichment process is as follows：The nitrate containing Pd, Ag or Pt or chlorination saline solution that mass fraction is 5%～28% are prepared, then the metal salt solution for preparing is mixed with MTBE, metal salt solution is 0.1～0.3 with the volume ratio of MTBE：1, under the conditions of 10 DEG C～40 DEG C, 35min～85min is stirred with the agitator that rotating speed is 400 revs/min～650 revs/min, stratification separates water phase；Filter after analysis pure hydrochloric acid is added in water phase, water phase is 0.5～5.5 with the volume ratio of analysis pure hydrochloric acid：1, the solution after filtration is extracted with organic solvent, and extract is concentrated into after 0.5mL～1mL, the enrichment process of sulfide is completed.The present invention has preferable concentration effect to thioether class sulfide main in MTBE, especially chain molecule type sulfide.
Description
Technical field
The present invention relates to a kind of method for being enriched with sulfide in methyl tertiary-butyl ether, more particularly to
One kind is enriched with chain molecule type sulfide in methyl tertiary-butyl ether by complex reaction
Method.
Background technology
Methyl tertiary butyl ether(MTBE) (MTBE) is a kind of high octane gasoline component, its research octane number (RON) RON
For 118, motor octane number MON is 100, is excellent gasoline high-octane rating additive and antidetonator.
Can there is no lamination with gasoline in MTBE, when reconciling with gasoline component, have good so that arbitrary proportion dissolves each other
Good mediation effect, the octane number that reconciles are higher than its clear octane number.MTBE oxygen content is of a relatively high, Neng Gouxian
Work improves motor vehicle exhaust emission, reduces CO contents in aerofluxuss, while reducing gasoline production cost.But,
MTBE meeting polluted underground water sources are studies have found that, therefore some states of the U.S. start to limit the use of MTBE.But
So far, Europe and Asia there is no the purpose of disabling MTBE, and over a period to come, MTBE will
Continue to become the key component of clean gasoline.
Typically not as product index, main cause is quality of gasoline standard after mediation to the sulfur content of MTBE
In it is less demanding to sulfur content.But with the enforcement of state's V vehicle emission standards, state's V content of sulfur in gasoline
The upper limit have already decreased to 10ppm, in order to reduce the sulfur content in gasoline, except exploitation reduce gasoline itself
Sulfur content outside, while be also required to reduce various additives in sulfur content, masters of the MTBE as blended gasoline
Want addO-on therapy, it is also desirable to reduce the sulfur content of MTBE.If sulfur content is higher in additive, having can
During blended gasoline can be caused, sulfur content is exceeded, and the product quality to gasoline is caused to have a strong impact on by this.
Sulfide in MTBE is mainly derived from upstream liquefied gas process, and the type of sulfide is mainly thioether
Class sulfide, also a small amount of mercaptan and thiophene-type sulfide.The sulfide removed in MTBE can lead to
The amount for reducing sulfide in liquefied gas is crossed realizing, but as catalytically cracked material increasingly becomes weight, so as to cause
Liquefied gas sulfur content gradually increases, though the sulfur content in desulfurization process, liquefied gas is often still higher.
At present, the process to sulfide in MTBE is mainly removed, but how not rich literature research is
Collection MTBE in sulfide and qualitative sulfide type, do not have sulfur speciation (structure of sulfide and
Type) distribution situation support, the removing for often resulting in sulfide in MTBE is not ideal enough.
Sulfide in MTBE can pass through the method removing of refined, adsorptive distillation and absorption.
The method that CN102757316A discloses sulfide in a kind of use activated carbon removing methyl tertiary butyl ether(MTBE).Should
Method is in a kettle. or in fixed bed, by activated carbon and raw material methyl tertiary butyl ether(MTBE) specific medium,
Refining reaction under the conditions of temperature and pressure, to reduce the sulfur content in methyl tertiary butyl ether(MTBE).It is de- using the method
The sulfur compounds adsorption for removing obtains the mixing of the sulfide of pure (without non-sulphur impurity) in activated carbon, not
Thing.The method needs to carry out on reactor or reaction bed, and needs specific medium, temperature and pressure bar
Part, therefore higher experimental cost need to be put into, and operational process of craft is complicated, energy consumption is larger.
The method that CN102898286A discloses sulfide in a kind of adsorptive distillation removing MTBE, to boil
Point is higher than MTBE, and has the thing of stronger adsorptive selectivity to thioether, mercaptan and Carbon bisulfide and thiophene
Matter is adsorbent, under uniform temperature and process conditions, by sulfide selective absorption in MTBE in suction
In attached dose, using the method desulfurization of vacuum distilling.The adsorbent used by this method is N-formyl morpholine N, second
Morpholide, Methanamide, acetamide, or two of which, or the mixture by above material be equipped with appropriate
Activator is constituted.Activator is organic oxidizing agent, is benzoyl peroxide, methyl ethyl ketone peroxide, peroxidating
One kind in Ketohexamethylene, tertbutanol peroxide, the addition of activator account for adsorbent gross mass 0.1%～
0.5%.The method is primarily directed in art production process, realizes the desulfurization of high-volume MTBE, heavier
What is wanted is that, in subtractive process, sulfide has chemical reaction with adsorbent or activating agent, destroys sulfide
Original structure.
CN101643392 discloses a kind of method of desulphurizing methyl tertiary butyl ether with high sulphur content：By high sulfur-bearing
The methyl tertiary butyl ether(MTBE) of amount is placed in distillation column, by reboiler heat, keep bottom temperature be 90 DEG C～
120 DEG C, pressure be 0.08 ± 0.02MPa, tower top temperature be 69 DEG C～75 DEG C, pressure be 0.06 ±
0.02MPa, makes finished product steam from tower top and maintain the reflux for than for 1～10, sulfur product is reclaimed from bottom of towe.Should
Method is in a distillation column, to make MTBE from tower top by the different temperatures and pressure that set tower reactor and tower top
Steam, so as to reach the purpose of desulfurization.As can be seen here, the method needs specific device and strict technique
Condition, is directed to the larger situation of sample size, is not particularly suited for testing the enrichment of indoor sulfide；And adopt
When removing sulfide with the method, lower boiling sulfide can be steamed from tower top in company with MTBE, from bottom of towe
The sulfur product of recovery is the higher boiling sulfur compound in MTBE, even if the sulfide that analysis removing is obtained,
During MTBE can not be represented, actual sulfur speciation is distributed.
CN103145534A discloses sulfide in a kind of deep removal methyl tertiary-butyl ether
Method, process is as follows：(1) nitrate aqueous solution of preparing metal element Cu, Ag, Ni, nitrate exist
In solution, shared mass fraction is 0.05%～35%, then adds adsorbent, adsorbent in this solution
Dipping 30 minutes～90 minutes, filters to isolate adsorbent, then that adsorbent is warm at 100 DEG C～120 DEG C
Degree is lower to be dried to constant weight.(2) Cu containing metallic element, the adsorbent of the nitrate of Ag, Ni are obtained after being dried,
40%～68% salpeter solution of mass concentration is stirred at room temperature down and is loaded on adsorbent.(3) after the completion of loading
Adsorbent and methyl tertiary butyl ether(MTBE) react at 15 DEG C～40 DEG C, can be with deep removal methyl tertiary butyl ether(MTBE)
Sulfide.It is sorbent used for silica gel, SBA series and MCM Series Molecules sieve, can using 60 DEG C～
90 DEG C of nitrogen Jing the technique regeneration Posterior circle such as blow, take off, being dried and using.By-product after desulfurization is also adsorbed on
In the hole of adsorbent.After adsorbent is impregnated by the method with nitrate, salpeter solution is loaded under stirring at room temperature,
Reacted to remove sulfide with the adsorbent after the completion of load with methyl tertiary butyl ether(MTBE).The method main purpose is
Sulfide in removing MTBE.In the method, employ adsorbent to remove sulfide, in removing
During sulfide, adsorbent is by reacting come sulphur removal with sulfide, and adsorbent hole can also adsorb
Other impurity in MTBE (by-product after desulfurization is also adsorbed in the hole of adsorbent), that is to say, that
Non- sulphur impurity is mixed with the sulfur-bearing thing of removing, and, the sulfur method has changed the sulfuration of MTBE Central Plains
The structure and type of thing.
The method that above-mentioned patent all gives sulfide in removing MTBE, its final purpose is to obtain
The MTBE products of the MTBE of low sulfur content or not sulfur-bearing, the sulfide for not being further directed to remove enter
Row is separated and enrichment, so as to obtain more pure mixture of sulfides standard sample, in MTBE
The research of sulfur speciation distribution is worked with qualitative, quantitative.The presence of Major Sulfides in MTBE is studied further
The structure and type of form, i.e. sulfide, for determining desulfurization technical scheme and instructing sulfur removal technology to have
Important meaning.The method for qualitative analysis of generally sulfide has two kinds, i.e. standard substance (sulfide standard article)
Qualitative and gas chromatograph-mass spectrometer (GC-MS) (mass spectrum) is qualitative.Standard substance are qualitative, and accuracy is high, but price
Costliness, more restricts, and in MTBE, most of sulfide is commercially bought at all less than its standard substance；
Gas chromatograph-mass spectrometer (GC-MS) is one of qualitative tool conventional at present, but because of sulfide content in MTBE
It is little, at all cannot direct detection it is qualitative.Therefore separate in choice experiment room, be enriched with sulfide, to obtain
Sulfide sample is a very simple and easy to do and very effective approach.
At present, the enrichment method of the relevant sulfide that documents and materials are reported for work has two classes, and the first kind is using purging
The instrument and equipment such as trapping or solid-phase microextraction is enriched with to the sulfide in sample；Equations of The Second Kind is using chemistry
Method is enriched with to the sulfide in sample.
" purge and trap-GC-MS-SIM methods determine volatile sulfur compoundses in water ", Wu Ting,《Analysis examination
Test room》, the 4th phase of volume 26, page 54～57, in April, 2007.The document adopts purge ＆ trap
Preenrichment has been carried out to the Carbon bisulfide in water, methyl sulfide and dimethyl disulfide, gas chromatogram has been then introduced into
Detected in-GC-MS (GC-MS)；" headspace solid-phase microextraction-gas chromatography-mass spectrography
Determine Determination of Trace Volatile alkyl sulfur compounds in waste water ", Gan Li,《Analytical chemistry》, the 5th phase of volume 35,
Page 643～647, in May, 2007.The document establishes headspace solid-phase microextraction and gas chromatography-mass spectrum
The method that combination determines the Determination of Trace Volatile alkyl sulfur compounds in artificial swamp waste water.This two documents category
The first kind in documents and materials, i.e., first carried out to the target sulphide in testing sample using instrument and equipment pre-
After enrichment, GC-MS is reused qualitative.This two documents are entered to the sulfide in sample using instrument and equipment
Row preenrichment, its shortcoming are that instrument price is expensive, and method is difficult to be promoted, and the sample that the method is directed to is necessary
For aqueous systems, for sulfide scope be Carbon bisulfide, methyl sulfide, dimethyl sulfide and Methyl disulfide
Ether.
" composition analysis of sulfide in Russian direct steaming gasoline ", Yang Shuqing,《Mass spectrum journal》, the
The phase of volume 29 the 5th, page 306～310, in September, 2008.The document is similar to CN103145534A,
Which adopts PdCl2Ligand chromatography separation and concentration Russia direct steaming gasoline in sulfide, with gas chromatogram-
Pulsive flame photometric detector is ground to the structure of wherein monomer sulfide with GC-MS
Study carefully.The method is concretely comprised the following steps：1. the preparation of Palladous chloride ./silica gel chromatographic column:By 2g Palladous chloride .s be dissolved in from
Aqueous solution is made in sub- water, 40g silica gel is poured into wherein, it is quick to mix；Beaker is placed on electric furnace and is slowly dried
It is roasting, it is stirred continuously, evaporating water, makes Palladous chloride. be evenly distributed on Silica Surface, control firing rate, prevent
It is only overheated, after substantially dry, it is placed in Muffle furnace, in 200 DEG C of roast 24h；Burned silica gel is put
Room temperature is cooled in exsiccator, it is standby.2. sulfide coordinate chromatograph is separated:By 5g PdCl2/ silica gel loads color
In spectrum post, with 20ml normal hexane moistening chromatographic columns, take 1g oil samples and be added on post, treat on oil sample and silicagel column
When surface just flushes, covered with a small amount of silica gel.Add normal hexane to rinse saturation part, one is connect per 10ml
Fraction, and carry out chromatography, when detect distillate component in start to occur aromatic hydrocarbon after stop plus normal hexane；
Then use V (normal hexane)：V (chloroform)=1：1 mixed solvent rinses fragrant part and Containing Sulfur
Compound, connects a fraction per 5ml, determines the total sulfur content of each fraction, sour distillate is merged, is concentrated,
A small amount of diethylamine is added to carry out chromatography.The method is by adsorbent (silica gel of surface attachment Palladous chloride .)
Concentrated the sulfur-containing compound in sample, the major defect of the method is the process for concentrating sulfide
In, other impurity that adsorbent hole also can be in adsorption sample, that is to say, that be mixed with the sulfur-bearing thing of concentration non-
Sulphur impurity.
" the acid enrichment of organic sulfur compounds in gasoline and structural analyses ", Meng Qi,《Chemistry of fuel journal》,
The 6th phase of volume 34, page 753～756, in December, 2006.The document can be with strong acid using sulfide
Effect forms the property of ion-type or highly polar compound, using mixed acid, the method for two grades of extractings of normal hexane,
Sulfide is enriched in normal hexane from gasoline, allows enriched sample directly sulfur be carried out by GC-MS
Compound is structure-characterized, but the target sulphide that the method is directed to is mainly cyclic thioether and thiophene-based (enrichment sample
Sulfide in product based on five, six-membered cyclic thioether and thiophene derivant, object construction of this and acid extracting
It is consistent).
" synthesis of sulfide Methylsulfonium Salt and electron spray-high resolution mass spectrum analysis in straight-run diesel oil ", Pan Na,
《Analytical chemistry》, the 3rd phase of volume 38, page 413～416, in March, 2010.The document is four
Under the catalytic action of silver fluoborate, methyl derivative reaction is carried out to straight-run diesel oil with iodomethane so as in
Organic sulfur compound changes polarity stronger sulfonium salt, then with electron spray-Fourier Transform Ion cyclotron Resonance matter
Spectrometer is detected.The major defect of the method is also to have changed sample Central Plains sulfide in concentration process
Structure and type.
" separation and concentration and Structural Identification of sulfide in Russian atmospheric gas oil ", Yang Shuqing,《Analysis is surveyed
Examination journal》, the 3rd phase of volume 26, page 404～408, in May, 2007.The document is using liquid-solid
Adsorption charomatography isolates the saturation part in straight-run diesel oil and fragrant part, and both are mixed, 100ml is added to
Be furnished with the round-bottomed flask of electromagnetic agitation and reflux condensation mode system, increase iodic acid tetrabutyl ammonia and 60ml methanol-
(volume ratio is 1 to benzene:5) back flow reaction 120min, washing remove excessive oxidant, use liquid-solid chromatography
Isolated oxide and non-oxide.Non- oxide is standby.1,4- dioxane of the oxide with 30ml
It is transferred to 150ml to be furnished with the round-bottomed flask of electromagnetic agitation and condensing reflux system, adds reducing agent aluminum hydride
Lithium, under slow backflow reacts 120min, is transferred into in mixed liquor after the hydrochloric acid of Deca a small amount of 8%
In separatory funnel, washing removes excessive reducing agent, is isolated to thioether class concentrated solution.By between oxidant
Chlorine benzylhydroperoxide and methylene chloride 80ml are added in the non-oxide being previously obtained, room temperature reaction
150min.Reduction reaction solvent for use absolute ether 60ml, reducing agent lithium aluminium hydride reduction, recovery time 120
Min, obtains thiophene-based concentrated solution.The document separates sample using liquid-solid adsorption chromatography method, has a disadvantage in that
During separating sample, other impurity that adsorbent hole also can be in adsorption sample, that is to say, that isolate
Sample it is impure, impurity can be mixed with；And the method is time-consuming longer, the target sulphide which is directed to is non-chain
Thioether class (the author isolates pure thioether class sulfide using oxidation-reduction method, qualitative with GC-MS,
It was found that chain thioether).
Above-mentioned four documents are first carried out after concentration to sulfide in sample using chemical method, then
Qualitative analyses are carried out using GC-MS.In these documents, some can change sample Central Plains sulfide
Structure and type；The target sulphide that some are directed to is non-chain thioether class；Some then can containing in concentration
Non- sulphur impurity is mixed with sulfur thing.
The content of the invention
The method that the present invention provides sulfide in a kind of enrichment methyl tertiary-butyl ether, it is especially suitable
The sulfide of chain molecule type in enrichment methyl tertiary butyl ether(MTBE).
The method of sulfide in the enrichment methyl tertiary-butyl ether of the present invention, enrichment process are as follows：
The nitrate or chlorate for preparing Pd containing metallic element, Ag or Pt that mass fraction is 5%～28% is water-soluble
Then the metal salt solution for preparing is mixed by liquid with MTBE, and the metal salt solution is with MTBE's
Volume ratio is 0.1～0.3：1, under the conditions of 10 DEG C～40 DEG C, with rotating speed be 400 revs/min～650 turns/
The agitator stirring 35min～85min for dividing, stratification separate water phase；In water phase, add analysis pure
Filter after hydrochloric acid, water phase is 0.5～5.5 with the volume ratio of analysis pure hydrochloric acid：1, the solution after filtration is with organic
Solvent extraction, after filtration, solution and the volume ratio of extraction organic solvent are 4～40：1, extract is dense
After being reduced to 0.5mL～1mL, the enrichment process of sulfide is completed.
Described metallic element saline solution mass fraction is preferably 15%～23%.
Described water phase is preferably 1 with the volume ratio of analysis pure hydrochloric acid：1～4：1.
After described filtration, solution is preferably 25 with the volume ratio of extraction organic solvent：1～35：1.
Described slaine is preferably silver nitrate, Palladous chloride. or platinum chloride.
Preferably, described organic solvent is in the constituted group of hexamethylene, normal hexane and dichloromethane
One or more.
Described water phase is preferably 1 with the volume ratio of analysis pure hydrochloric acid：1～3：1.
After described filtration, solution is preferably 25 with the volume ratio of extraction organic solvent：1～32：1.
The enrichment method of the present invention is primarily directed to the chain molecule type sulfide in MTBE, these sulfur
Contain higher carbon number or multiple sulfur in the molecule of compound because there is no commercially available standard substance, can only using separating,
The method of enrichment enters mass spectrum after the content of sulfide is improved again carries out the determination of structure and type.Also, first
Sulfide in methyl tertiary butyl ether(MTBE) is enriched with, not only can be avoided because not having the suitable standard substance cannot
Realize qualitative, and the interference of non-thia mass peak can be eliminated during enrichment, play purification sulfuration
Thing, the purpose for improving sulfide content.
Beneficial effects of the present invention are：Using metal salt solution and the direct hybrid reactions of MTBE, it is to avoid
When adding adsorbent, other impurity in adsorbent absorption MTBE cause the sulfide being enriched with impure
Defect；Meanwhile, this method has used hydrochloric acid, hydrochloric acid make the product network of metal salt solution and sulfide
Close, thus overcome the defect of sulfide structure and type change in MTBE；Also, using organic
Solvent extraction, the balancing speed of phase are fast, good separating effect, the high income of object, easy realization simple to operate；
In present invention enrichment MTBE, chain molecule type sulfide does not contain non-sulphur impurity, the chain molecule type being enriched to
Sulfide content is high, can reach more than 70%.
In addition, this method is simple, quick, easy to operate, the enrichment to sulfide is targeted, and tests into
This low, energy consumption is little, directly can complete in laboratory, sample size is not also limited.
The present invention carries out purification, enrichment to sulfide, is that gas chromatograph-mass spectrometer (GC-MS) identifies its structure group
Into there is provided possible, application of the instrument in trace sulfide analysis field is expanded, while methyl tertiary butyl ether(MTBE)
Middle sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) manufacturer targetedly to determine desulfurization technology
Scheme, instructs sulfur removal technology.
Description of the drawings
Fig. 1 is PFPD (pulsive flame photometric detector) spectrums of sulfide in 1 gained pregnant solution of embodiment
Figure；
Fig. 2 is FID (flame ionization ditector) spectrogram of sulfide in 1 gained pregnant solution of embodiment；
Fig. 3 is 4 chain molecule type sulfide for peak number in 1～embodiment of embodiment, 8 gained pregnant solution
Mass spectrum rod figure；
Fig. 4 is standard spectrogram corresponding with Fig. 3 in mass spectrograph；
Fig. 5 is 2 chain molecule type sulfide for peak number in 1～embodiment of embodiment, 8 gained pregnant solution
Mass spectrum rod figure；
Fig. 6 is standard spectrogram corresponding with Fig. 5 in mass spectrograph；
Fig. 7 be pregnant solution obtained by 1～embodiment of embodiment 8 (except embodiment 4) in peak number for 6 chain
The mass spectrum rod figure of molecule-type sulfide；
Fig. 8 is standard spectrogram corresponding with Fig. 7 in mass spectrograph；
Fig. 9 is the PFPD spectrograms of sulfide in 2 gained pregnant solution of embodiment；
Figure 10 is the FID spectrograms of sulfide in 2 gained pregnant solution of embodiment；
Figure 11 is the PFPD spectrograms of sulfide in 3 gained pregnant solution of embodiment；
Figure 12 is the FID spectrograms of sulfide in 3 gained pregnant solution of embodiment；
Figure 13 is the PFPD spectrograms of sulfide in 4 gained pregnant solution of embodiment；
Figure 14 is the FID spectrograms of sulfide in 4 gained pregnant solution of embodiment；
Figure 15 is the PFPD spectrograms of sulfide in 6 gained pregnant solution of embodiment 5 and embodiment；
Figure 16 is the FID spectrograms of sulfide in 6 gained pregnant solution of embodiment 5 and embodiment；
Figure 17 is the PFPD spectrograms of sulfide in 8 gained pregnant solution of embodiment 7 and embodiment；
Figure 18 is the FID spectrograms of sulfide in 8 gained pregnant solution of embodiment 7 and embodiment.
Wherein, 1 is ethyl sulfide (CH3CH2SCH2CH3), 2 be methyl ethyl sulfide (CH3SCH2CH3)、
3 is dimethyl disulfide (CH3SSCH3), 4 be Methylethyl disulfide (CH3SSCH2CH3)、5
For 2- methyl -2- methyl butyl sulfide ((CH3)2C(CH3S)CH2CH3), 6 be diethyl disulphide
(CH3CH2SSCH2CH3), 7 be dimethyl sulphur-based ethane ((CH3S)2CHCH3), 8 be dimethyl
Trithioether (CH3SSSCH3), 9 be 2,2- dimethyl sulphur-based propane (CH3C(CH3S)2CH3), 10 be
Four thioether (CH of dimethyl3SSSSCH3), 11 be diethyl trithioether (CH3CH2SSS CH2CH3)、
12 is solvent peak.
Specific embodiment
The present invention is further illustrated by the following examples, but the present invention is not limited to these embodiments.
MTBE used by the present invention takes from Golmud oil plant of Petrochina Qi Nghai Oilfield Company, institute
Silver nitrate, Palladous chloride., platinum chloride, hydrochloric acid, hexamethylene, normal hexane and dichloromethane are commercially available
Analytical reagent, the present invention used by instrument be：Eurostar's agitator of German IKA companies production and
The 7890-5775 gas chromatograph-mass spectrometers of Agilent companies of U.S. production.Gas chromatogram used by the present invention
- GC-MS possesses full scan and selectivity ion scan function, composes storehouse with NIST98, and detector is sensitive
Degree S/N ＞ 600:1 (1pg octafluoro naphthalenes, full scan).
Embodiment 1
(1) enrichment process
The silver nitrate aqueous solution 20mL that mass fraction is 21% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, and silver nitrate aqueous solution is 0.2 with the volume ratio of MTBE：1, when temperature is 15 DEG C,
After with the agitator stirring mixed solution 80min that rotating speed is 650 revs/min, stratification separates water phase.
Concentrated hydrochloric acid 15mL is added in water phase, water phase is 1.2 with the volume ratio of concentrated hydrochloric acid：1, the solution is filtered,
Solution after filtration is extracted with organic solvent dichloromethane, is extracted 1 time, extraction consumption is 1mL,
After filtration, solution and the volume ratio of extraction organic solvent are 30：1, extract is concentrated into into 0.5mL, it is complete
The enrichment process of sulphidisation.
(2) oxide morphology qualification process
Take 0.2 μ L samples import gas chromatograph-mass spectrometer (GC-MS), sample Jing chromatographic system separation after, 70
Electron-volt bombardment is lower to be ionized, and forms a series of different abundance, the fragment peak of different charge-mass ratios, obtains being reflected
Determine the mass spectrum rod figure of sulfide, referring to shown in Fig. 3, Fig. 5 and Fig. 7, standard spectrum corresponding with mass spectrograph
Figure Fig. 4, Fig. 6 and Fig. 8 are contrasted, you can it is determined that being enriched to the structure and composition of sulfide.The qualitative determinations of Jing
Chain molecule type sulfide it is entitled：Ethyl sulfide (CH3CH2SCH2CH3)；Methyl ethyl sulfide
(CH3SCH2CH3)；Dimethyl disulfide (CH3SSCH3)；Methylethyl disulfide
(CH3SSCH2CH3)；2- methyl -2- methyl butyl sulfide ((CH3)2C(CH3S)CH2CH3)；Diethyl
Base disulfide (CH3CH2SSCH2CH3)；Dimethyl sulphur-based ethane ((CH3S)2CHCH3)；Dimethyl
Trithioether (CH3SSSCH3)；2,2- dimethyl sulphur-based propane (CH3C(CH3S)2CH3)；Four sulfur of dimethyl
Ether (CH3SSSSCH3)；Diethyl trithioether (CH3CH2SSS CH2CH3)。
Fig. 1 and Fig. 2 is respectively PFPD the and FID spectrograms of sulfide in 1 gained pregnant solution of embodiment,
In Fig. 1, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Fig. 1, Fig. 2
It is the sulfide without non-sulphur impurity that contrast can be seen that the sample being enriched to, and predominantly chain molecule type
Sulfide, its content up to more than 80%.
In embodiment 1, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 11 in sulfide structure, expanded instrument trace sulfide analyze
The application in field, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to give birth to
Produce producer and targetedly determine desulfurization technical scheme, instruct sulfur removal technology.
Embodiment 2
Platinum chloride aqueous solution 20mL that mass fraction is 12% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, when temperature is 35 DEG C, with the agitator stirring mixed solution that rotating speed is 550 revs/min
After 35min, stratification separates water phase, and concentrated hydrochloric acid 9mL is added in water phase.Other test procedures with
Embodiment 1 is identical.
Fig. 9 and Figure 10 is respectively PFPD the and FID spectrograms of sulfide in 2 gained pregnant solution of embodiment,
In fig .9, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Fig. 9, Figure 10
Contrast as can be seen that the sample that is enriched to is the sulfide without non-sulphur impurity, and predominantly chain molecule
Type sulfide, its content up to more than 70%.
In example 2, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 4 in sulfide structure, expanded instrument trace sulfide analysis lead
The application in domain, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to produce
Producer targetedly determines desulfurization technical scheme, instructs sulfur removal technology.
Embodiment 3
The palladium chloride aqueous solution 20mL that mass fraction is 16% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, when temperature is 20 DEG C, with the agitator stirring mixed solution that rotating speed is 450 revs/min
After 60min, stratification separates water phase, and concentrated hydrochloric acid 13mL is added in water phase.Other test procedures
It is same as Example 1.
Figure 11 and Figure 12 is respectively PFPD the and FID spectrograms of sulfide in 3 gained pregnant solution of embodiment,
In fig. 11, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Figure 11, figure
12 contrast is as can be seen that the sample that is enriched to is the sulfide without non-sulphur impurity, and predominantly chain
Molecule-type sulfide, its content up to more than 70%.
In embodiment 3, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 7 in sulfide structure, expanded instrument trace sulfide analysis lead
The application in domain, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to produce
Producer targetedly determines desulfurization technical scheme, instructs sulfur removal technology.
Embodiment 4
The palladium chloride aqueous solution 30mL that mass fraction is 5% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, when temperature is 30 DEG C, with the agitator stirring mixed solution that rotating speed is 500 revs/min
After 70min, stratification separates water phase, adds concentrated hydrochloric acid 5mL, filter this solution in water phase, will
Solution after filtration is extracted with organic solvent hexamethylene, is extracted 1 time, and extraction consumption is 2mL, will
Extract is concentrated into 1mL, completes the enrichment process of sulfide.
Figure 13 and Figure 14 is respectively PFPD the and FID spectrograms of sulfide in 4 gained pregnant solution of embodiment,
In fig. 13, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Figure 13, figure
14 contrast is as can be seen that the sample that is enriched to is the sulfide without non-sulphur impurity, and predominantly chain
Molecule-type sulfide, its content up to more than 75%.
In example 4, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 3 in sulfide structure, expanded instrument trace sulfide analysis lead
The application in domain, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to produce
Producer targetedly determines desulfurization technical scheme, instructs sulfur removal technology.
Embodiment 5
Platinum chloride aqueous solution 30mL that mass fraction is 7% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, when temperature is 10 DEG C, with the agitator stirring mixed solution that rotating speed is 650 revs/min
After 85min, stratification separates water phase, and concentrated hydrochloric acid 7mL is added in water phase.Other test procedures with
Embodiment 4 is identical.
Figure 15 and Figure 16 is respectively PFPD the and FID spectrograms of sulfide in 5 gained pregnant solution of embodiment,
In fig .15, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Figure 15, figure
16 contrast is as can be seen that the sample that is enriched to is the sulfide without non-sulphur impurity, and predominantly chain
Molecule-type sulfide, its content up to more than 75%.
In embodiment 5, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 5 in sulfide structure, expanded instrument trace sulfide analysis lead
The application in domain, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to produce
Producer targetedly determines desulfurization technical scheme, instructs sulfur removal technology.
Embodiment 6
The silver nitrate aqueous solution 30mL that mass fraction is 9% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, when temperature is 40 DEG C, with the agitator stirring mixed solution that rotating speed is 400 revs/min
After 40min, stratification separates water phase, and concentrated hydrochloric acid 11mL is added in water phase.Other test procedures
It is same as Example 4.
Figure 15 and Figure 16 is respectively PFPD the and FID spectrograms of sulfide in 6 gained pregnant solution of embodiment,
In fig .15, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Figure 15, figure
16 contrast is as can be seen that the sample that is enriched to is the sulfide without non-sulphur impurity, and predominantly chain
Molecule-type sulfide, its content up to more than 75%.
In embodiment 6, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 5 in sulfide structure, expanded instrument trace sulfide analysis lead
The application in domain, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to produce
Producer targetedly determines desulfurization technical scheme, instructs sulfur removal technology.
Embodiment 7
Platinum chloride aqueous solution 10mL that mass fraction is 25% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, when temperature is 10 DEG C, with agitator (rotating speed is 400 revs/min) stirring mixed solution
After 50min, stratification separates water phase.Concentrated hydrochloric acid 9mL is added in water phase, this solution is filtered, will
Solution after filtration is extracted with organic solvent-normal hexane, is extracted 1 time, and extraction consumption is 3mL, will
Extract is concentrated into 0.7mL, completes the enrichment process of sulfide.
Figure 17 and Figure 18 is respectively PFPD the and FID spectrograms of sulfide in 7 gained pregnant solution of embodiment,
In fig. 17, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Figure 17, figure
18 contrast is as can be seen that the sample that is enriched to is the sulfide without non-sulphur impurity, and predominantly chain
Molecule-type sulfide, its content up to more than 70%.
In embodiment 7, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 7 in sulfide structure, expanded instrument trace sulfide analysis lead
The application in domain, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to produce
Producer targetedly determines desulfurization technical scheme, instructs sulfur removal technology.
Embodiment 8
The palladium chloride aqueous solution 10mL that mass fraction is 28% is prepared, by this solution and the methyl- tert of 100mL
Butyl ether mixes, when temperature is 25 DEG C, with agitator (rotating speed is 500 revs/min) stirring mixed solution
After 75min, stratification separates water phase, and concentrated hydrochloric acid 13mL is added in water phase.Other test procedures
It is same as Example 7.
Figure 17 and Figure 18 is respectively PFPD the and FID spectrograms of sulfide in 8 gained pregnant solution of embodiment,
In fig. 17, the chromatographic peak for indicating numeral is the chromatographic peak of chain molecule type sulfide.From Figure 17, figure
18 contrast is as can be seen that the sample that is enriched to is the sulfide without non-sulphur impurity, and predominantly chain
Molecule-type sulfide, its content up to more than 70%.
In embodiment 8, by the purification of sulfide, enrichment in pregnant solution so that gas chromatogram-matter
Spectrum combined instrument identify in pregnant solution 7 in sulfide structure, expanded instrument trace sulfide analysis lead
The application in domain, at the same in methyl tertiary butyl ether(MTBE) sulfide it is accurate qualitative, be conducive to methyl tertiary butyl ether(MTBE) to produce
Producer targetedly determines desulfurization technical scheme, instructs sulfur removal technology.
The present invention is not limited for the model of gas chromatograph-mass spectrometer (GC-MS), it is adaptable to various models
Gas chromatograph-mass spectrometer (GC-MS).
Certainly, the present invention can also have other various embodiments, without departing substantially from spirit of the invention and its essence
In the case of, those of ordinary skill in the art can make various corresponding changes and change according to the present invention
Shape, but these corresponding changes and deformation should all belong to protection scope of the present invention.
Claims (8)
1. it is a kind of enrichment methyl tertiary-butyl ether in sulfide method, it is characterised in that enrichment
Process is as follows：Prepare mass fraction be 5%～28% Pd containing metallic element, Ag or Pt nitrate or
Then the metal salt solution for preparing is mixed by chlorination saline solution with MTBE, the metal salt solution
Volume ratio with MTBE is 0.1～0.3：1, under the conditions of 10 DEG C～40 DEG C, with rotating speed be 400 turns/
～650 revs/min of agitator stirring 35min～85min, stratification is divided to separate water phase；In water phase
Filter after adding analysis pure hydrochloric acid, water phase is 0.5～5.5 with the volume ratio of analysis pure hydrochloric acid：1, after filtration
Solution is extracted with organic solvent, and after filtration, solution and the volume ratio of extraction organic solvent are 4～40：1,
Extract is concentrated into after 0.5mL～1mL, the enrichment process of sulfide is completed.
2. method according to claim 1, it is characterised in that described metallic element saline solution quality
Fraction is 15%～23%.
3. method according to claim 1, it is characterised in that described water phase and analysis pure hydrochloric acid
Volume ratio is 1：1～4：1.
4. method according to claim 1, it is characterised in that solution is used with extraction after described filtration
The volume ratio of organic solvent is 25：1～35：1.
5. method according to claim 1, it is characterised in that described slaine is silver nitrate, chlorine
Change palladium or platinum chloride.
6. method according to claim 1, it is characterised in that described organic solvent selected from hexamethylene,
One or more in normal hexane and the constituted group of dichloromethane.
7. method according to claim 1, it is characterised in that described water phase and analysis pure hydrochloric acid
Volume ratio be 1：1～3：1.
8. method according to claim 1, it is characterised in that solution and extraction after described filtration
It is 25 with the volume ratio of organic solvent：1～32：1.
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| CN103145534A (en) * | 2013-03-26 | 2013-06-12 | 南开大学 | Method for deeply removing sulfides in gasoline additive, namely methyl tert-butyl ether |
| CN104807895A (en) * | 2014-01-27 | 2015-07-29 | 中国石油化工股份有限公司 | Method for analyzing distribution of sulfur in methyl tert-butyl ether, sulfide qualitative analysis database, and use of database |
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