CN102086403A - Method for extracting and desulfurizing oxidated diesel oil - Google Patents
Method for extracting and desulfurizing oxidated diesel oil Download PDFInfo
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- CN102086403A CN102086403A CN2009102166104A CN200910216610A CN102086403A CN 102086403 A CN102086403 A CN 102086403A CN 2009102166104 A CN2009102166104 A CN 2009102166104A CN 200910216610 A CN200910216610 A CN 200910216610A CN 102086403 A CN102086403 A CN 102086403A
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Abstract
The invention relates to a method for extracting and desulfurizing oxidated diesel oil, which comprises the following steps: after removing water and a catalyst, extracting the oxidated diesel oil by using methanol as extracting agent; extracting for a plurality of times, and mixing the extracting agent and oxidated diesel oil according to a volume ratio of 1.0 at each time; at a temperature of 35 to 42 DEG C, stirring the mixture for 3 to 6 minutes, and transferring the mixture to a separating funnel; and after demixing, separating the extracting agent to obtain a desulfurized diesel oil product. The method is low in investment and operation cost, and is easy to operate and control.
Description
Technical field
The present invention relates to a kind of straight-run diesel oil sulfur method, specifically be meant a kind of oxidated diesel oil extraction desulphurization method.
Background technology
Abstraction desulfurization is to select appropriate solvent with the organic sulfide effective elimination in the oil product.Generally, it can effectively remove the mercaptan in the oil product, by distillation extraction solvent is separated with mercaptan again.Usually use the alkali lye extraction agent.The most attracting feature of abstraction desulfurization is to operate under low temperature, low pressure.Mixing tank even operation at room temperature.This technology can not change the chemical structure of oil fuel component.Because employed equipment does not have special requirement, this technology is easy to use at refinery.In order to make this technology effective, carefully the slective extraction agent is to satisfy many requirements.Organic sulfide must have high solvability in extraction agent, extraction agent must have the boiling point different with sulfocompound, and solvent must be cheap in to guarantee the economic and practical of this technology.After tested have solvent of different nature, with the difference of extraction times, acetone, ethanol, polyoxyethylene glycol and nitrogen-containing solvent demonstrate rational desulfuration efficiency (50-90%).
Summary of the invention
Technical problem to be solved by this invention provides a kind of oxidated diesel oil extraction desulphurization method, it not only invest and working cost low, and the operation and control get up to be easier to.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the oxidated diesel oil extraction desulphurization method may further comprise the steps:
(1) remove anhydrate and catalyzer after, oxidated diesel oil extracts as extraction agent with methyl alcohol;
(2) extraction several times, each extraction agent and oxidated diesel oil 1.0 mix by volume;
(3) under 35～42 ℃ of temperature, mixture is transferred in the separating funnel after stirring 3～6min;
(4) treat layering after, promptly obtain the desulfurized diesel oil product after will extraction liquid separating;
(5) treated oil is poured into weighing its Mass Calculation mass yield in the fine taper bottle that weighing got well.
In order to reach better effect, extraction times is twice in the described step 2; Churning time is 5min the best in the described step 3; Temperature is 40 ℃ in the described step 3.
To sum up, the invention has the beneficial effects as follows: operate under low temperature, the low pressure condition and carry out, even mixing tank can operate at normal temperatures and pressures, so its investment and working cost are low, operation and control are easily.This process does not change the chemical structure of the chemical composition of oil fuel, compares with other technologies, has great advantage economically.
Description of drawings
Fig. 1 is the abstraction desulfurization simplified flow chart.
Fig. 2 is the influence of agent oil volume comparison sweetening effectiveness.
Fig. 3 is the influence of extraction times to effect of extracting.
Fig. 4 is that the extraction time is to taking off the influence of effect.
Fig. 5 is the influence of extraction temperature to desulfurization degree.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment
(1) the extraction principle of polarity sulfide
Abstraction desulfurization is according to the similar principle that mixes of solvent extraction.Because the polarity of HYDROCARBONS IN DIESEL OIL compound and non-hydrocarbon compound has difference, particularly pass through after the selective oxidation, sulfide in diesel oil has generated stronger sulfone (or sulfoxide) class of polarity, select a kind of solvent, according to the similar principle that mixes, sulfocompounds such as sulfone class are different with the partition ratio in the diesel oil at solvent, and choice of Solvent is strong more, the partition ratio difference is big more, easy more being removed.Adopting solvent-extracted method is exactly to make sulfone compound in the diesel oil enter solvent phase and be removed, and reaches the purpose of desulfurization.
(2) extracting process
Remove anhydrate and catalyzer after, oxidated diesel oil extracts as extraction agent with methyl alcohol; Extraction several times, each extraction agent and oxidated diesel oil 1.0 mix by volume; Under 35～42 ℃ of temperature, mixture is transferred in the separating funnel after stirring 3～6min; After treating layering, will promptly obtain the desulfurized diesel oil product after the extraction liquid separation.Pour treated oil in the fine taper bottle that weighing got well weighing its Mass Calculation mass yield.
The calculating of desulfurization degree and mass yield:
Sulphur content * 100% before desulfurization degree/%=(sulphur content before the desulfurization after the sulphur content-desulfurization of diesel oil)/desulfurization
Mass yield/%=(quality of the quality/raw material of diesel oil after the desulfurization) * 100%
(3) selection of extraction conditions
Organic solvent can both extract the sulfone class in the diesel oil after the oxidation like many and the sulfone class polar phase, and methyl alcohol has been investigated in this test, acetonitrile, ethylene glycol, the abstraction desulfurization effect of ethanol and 5% alkali-five kinds of organic solvents of methyl alcohol.The character of reagent sees Table 1.
The character of table 1 extraction agent
1) extraction agent is preferred
Experiment with oxidation after diesel oil be raw material, with H
2O
2/ CH
3Diesel oil after the oxidation of COOH system is made as diesel oil A, is made as diesel oil B with diesel oil after the Fenton reagent oxidation, investigates the effect of extracting of several extraction agents, and experimental data is seen Fig. 2.Experiment condition: agent oil volume ratio is 1.0, and extraction times is 1, and extraction temperature is 25 ℃, and the extraction time is 5min.
The various extraction agents of table 2 are to the influence of effect of extracting
From table 2 data as can be seen, to carrying out solvent extraction behind the diesel oil oxidation, methyl alcohol and 5% alkali-two kinds of solvents of methyl alcohol all have bigger desulfurization degree (for not being 83.8% and 83.1%) to diesel oil A, the a little higher than methyl alcohol of the desulfurization degree of 5% alkali-methyl alcohol, explanation adds the selectivity that alkali has improved abstraction desulfurization in methyl alcohol, and methyl alcohol to diesel oil A mass yield far above 5% alkali-methyl alcohol, though though ethylene glycol and acetonitrile are higher to diesel oil A mass yield, desulfurization degree is far below methyl alcohol and 5% alkali-methyl alcohol.Methyl alcohol and acetonitrile all have bigger desulfurization degree (being respectively 74.2% and 73.8%) to diesel oil B, but the mass yield of methyl alcohol is higher than acetonitrile, and comprehensive each side factor considers that it is extraction solvent that two oxidation systems of this experiment all adopt methyl alcohol.
2) selection of extraction agent consumption
Diesel oil is raw material after the experiment oxidation, is being under the condition of extraction agent with methyl alcohol, is that the volume ratio of diesel oil is investigated after solvent and the oxidation to the consumption of extraction solvent, and solvent load is seen Fig. 2 to the experimental result of the influence of desulfurization degree and diesel quality yield.
As seen from Figure 2, diesel oil solvent extraction desulfurization degree, is thought than increasing with the agent oil volume after the oxidation, and this may be that solvent load is big, and the concentration of sulfide in extraction agent reduces, and mass transfer force is increasing.Will consider the requirement of desulfurization degree in order to obtain the best solvent consumption, though the agent oil volume has than high desulfurization rate than increasing, the increase of toner oil volume ratio descends the diesel quality yield, also can make the raw material processing power reduce the also corresponding raising of process cost simultaneously.Therefore, require to determine that according to feedstock property and quality product agent oil volume ratio is 1: 1, the desulfurization degree of diesel oil A is 76.6%, and mass yield is 98.6%; The desulfurization degree of diesel oil B is 86.8%, and mass yield is 97.8%.
3) extraction times is to the influence of effect of extracting
Fig. 3 is diesel fuel desulfurization rate and the mass yield variation relation with extraction times., extraction agent is divided into 1 time, 2 times and 3 times adds in the diesel oil than being under 1.0 the condition in total agent oil volume, investigate the influence of extraction times, other experiment condition: normal temperature, extraction time 2min desulfurization degree and diesel quality yield.
As seen from Figure 3, the desulfurization degree of methanol extraction agent all increases with the increase of extraction times, but increases seldom for the third time, and the diesel quality yield all descends with the increase of extraction times, and it is few to descend for the second time, and it is obvious to descend for the third time.Slave unit expense and process cost are considered, extraction times is too much unsuitable, otherwise can increase process cost and facility investment, takes all factors into consideration desulfurization degree, diesel quality yield and equipment, process cost, in total agent oil volume than being that 2 times effect of extracting is better under the 1 constant condition.
4) selection of extraction time
Diesel oil is raw material after the experiment oxidation, is being under the condition of extraction solvent with methyl alcohol, and agent oil volume ratio is extraction 2 times under 1: 1 the ratio room temperature, investigates the influence of extraction time to sweetening effectiveness, sees Fig. 4.
As seen from Figure 4, there is less influence the extraction time to desulfurization degree, along with the amount that sulfocompound in the diesel oil within prolongation 1～5min of extraction time is dissolved in the extraction agent is amid a sharp increase, does not have considerable change after the 5min.Unsuitable long with this extraction time, the slective extraction time is 5min.
5) selection of extraction temperature
The dissolving power of temperature effect solvent and selectivity.At a certain temperature, the solubleness of solvent is certain.Experiment with oxidation after diesel oil be raw material, be under the condition of extraction solvent with methyl alcohol, agent oil volume ratio is extraction 2 times under 1: 1 the ratio room temperature, extraction 5min.Investigate the influence of extraction temperature, see Fig. 5 sweetening effectiveness.
As seen from Figure 5, the methyl alcohol desulfurization degree increases earlier with the temperature rising and afterwards descends, and sweetening effectiveness is best near the temperature range 40 ℃, and this moment, the desulfurization degree of diesel oil A was 82%, and sulphur content is 125 μ g/g; The desulfurization degree of diesel oil B is 97%, and sulphur content is 21 μ g/g, is extraction temperature to select 40 ℃ in this experiment afterwards.
As mentioned above, just can realize the present invention preferably.
Claims (4)
1. the oxidated diesel oil extraction desulphurization method is characterized in that, may further comprise the steps:
(1) remove anhydrate and catalyzer after, oxidated diesel oil extracts as extraction agent with methyl alcohol;
(2) extraction several times, each extraction agent and oxidated diesel oil 1.0 mix by volume;
(3) under 35～42 ℃ of temperature, mixture is transferred in the separating funnel after stirring 3～6min;
(4) treat layering after, promptly obtain the desulfurized diesel oil product after will extraction liquid separating.
2. oxidated diesel oil extraction desulphurization method according to claim 1 is characterized in that, extraction times is twice in the described step 2.
3. oxidated diesel oil extraction desulphurization method according to claim 1 is characterized in that, churning time is 5min in the described step 3.
4. oxidated diesel oil extraction desulphurization method according to claim 1 is characterized in that, temperature is 40 ℃ in the described step 3.
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| CN2009102166104A CN102086403A (en) | 2009-12-07 | 2009-12-07 | Method for extracting and desulfurizing oxidated diesel oil |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881749A (en) * | 2014-03-24 | 2014-06-25 | 南开大学 | Method for removing thiophenic sulfide in fuel oil |
| CN114292668A (en) * | 2021-12-21 | 2022-04-08 | 镇江市高等专科学校 | Oxidation treatment method for fuel oil deep desulfurization process |
-
2009
- 2009-12-07 CN CN2009102166104A patent/CN102086403A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103881749A (en) * | 2014-03-24 | 2014-06-25 | 南开大学 | Method for removing thiophenic sulfide in fuel oil |
| CN114292668A (en) * | 2021-12-21 | 2022-04-08 | 镇江市高等专科学校 | Oxidation treatment method for fuel oil deep desulfurization process |
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Application publication date: 20110608 |