CN106866616A - A kind of method for preparing thiophene-type sulfide - Google Patents
A kind of method for preparing thiophene-type sulfide Download PDFInfo
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- CN106866616A CN106866616A CN201710090098.8A CN201710090098A CN106866616A CN 106866616 A CN106866616 A CN 106866616A CN 201710090098 A CN201710090098 A CN 201710090098A CN 106866616 A CN106866616 A CN 106866616A
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- thiophene
- type sulfide
- chloride
- metal chloride
- fuel oil
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
- C07D333/10—Thiophene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/08—Hydrogen atoms or radicals containing only hydrogen and carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
- C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
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- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a kind of method for preparing thiophene-type sulfide, methods described comprises the following steps：1) fuel oil is mixed with metal chloride stirring, the solid-liquid suspension is separated off fuel oil by reaction generation thiophenic sulfur metal chloride suspension, obtains thiophenic sulfur metal chloride；2) solvent of dissolving metal chloride is added in the thiophenic sulfur metal chloride, stirring obtains the oil phase containing thiophene-type sulfide and the water phase containing metal chloride, and by the oil phase and the aqueous phase separation；3) oil phase containing thiophene-type sulfide is carried out into rectifying, obtains thiophene-type sulfide.The present invention finally can extract out different types of thiophene-type sulfide with fuel oil as raw material from fuel oil, and extraction efficiency is high, and the purity of thiophene-type sulfide product is high, and preparation method of the present invention stabilization is practical.
Description
Technical field
The invention belongs to fuel oil manufacture field, more particularly to a kind of method for preparing thiophene-type sulfide.
Background technology
China is the big oil consumption country of the first in the world, and the Apparent con- sumption of 2015 has reached 5.34 hundred million tons, and is in still
Reveal up-trend.The main purpose of PETROLEUM PROCESSING is that the combustion of different qualities is obtained by means such as distillation, catalytic cracking, hydrogenation
Material oil.For fuel oil, wherein containing various thiophene-type sulfides, such as thiophene (T), monomethyl thiophene (MT), dimethyl
Thiophene (DMT), benzothiophene (BT), monomethyl benzothiophene (MBT), dimethyl benzothiophene (DMBT) etc..Generally, these thiophenes
Fen class sulfide is considered pollution sources, before fuel oil use, thiophenic sulfur need to be removed from oil by sulfur removal technology.Example
Such as, industry-wide hydrodesulfurization technology, is exactly to use H2As reactant, deposited in HTHP, and catalyst
Under the conditions, thiophenic sulfur is converted into hydrocarbon and H2S, so as to realize the desulfurization of oil product.In addition, S-Zorb techniques
It is conventional fuel desulfuration technology, the technology is in H2In the presence of, using adsorbent (such as ZnO-NiO) by the sulphur atom in thiophenic sulfur
Directly adsorb, form ZnS, reuse high temperature air and ZnS is converted into ZnO and SO2, realize the regeneration of adsorbent and taking off for sulphur
Remove.Organic thiophenic sulfur by chemical reaction, is converted into inorganic H by above-mentioned two technologies2S or SO2。
However, thiophenic sulfur class sulfide itself just has value very high, the sterling price of such as thiophenes sulfides just exists
100-5000 yuan/kilograms.In addition, the derivative of thiophenic sulfur is even more widely used in fields such as medicine, dyestuff, conductive materials.Example
Such as, 2- thiophene acetic acids and 2- thiophen acetyl chlorides can be used as the intermediates of production Antibiotics medicine cephaloridnum.Polythiophene, poly- 3-
Methylthiophene is widely used in conductive material.2,3- dimethyl sulphur-baseds benzothiophene has important in synthesis organic conductive Material Field
Using.It follows that by chemical reaction, the thiophenic sulfur of high value to be converted into the H of low value2S or SO2, it is actually a kind of
The waste of resource.Therefore, if separation and Extraction goes out thiophene-type sulfide from large consumer goods fuel oil, well should will have
Use prospect.
The content of the invention
For drawbacks described above of the prior art, thiophene-type sulfide is prepared it is a primary object of the present invention to provide one kind
Method, with fuel oil as raw material, separation and Extraction has gone out thiophene-type sulfide from fuel oil.
In order to achieve the above object, the present invention is adopted the following technical scheme that：A kind of method for preparing thiophene-type sulfide, institute
The method of stating comprises the following steps：
1) fuel oil is mixed with metal chloride stirring, reaction generation thiophenic sulfur-metal chloride suspension will be described
Solid-liquid suspension is separated off fuel oil, obtains thiophenic sulfur-metal chloride；
2) solvent of dissolving metal chloride is added in the thiophenic sulfur-metal chloride, stirring is obtained containing thiophene-based
The oil phase of sulfide and the water phase containing metal chloride, and by the oil phase and the aqueous phase separation；
3) oil phase containing thiophene-type sulfide is carried out into rectifying, obtains thiophene-type sulfide.
As further preferably, the fuel oil is selected from oil product of the boiling range at 70 DEG C -350 DEG C, in the fuel oil
Sulfur content is 100-10000 μ g/g.
As further preferably, the thiophene-type sulfide is selected from thiophene, monomethyl thiophene, thioxene, benzo
Thiophene, monomethyl benzothiophene and dimethyl benzothiophene.
As further preferably, the metal chloride is selected from anhydrous Aluminum chloride, anhydrous ferric chloride, anhydrous protochloride
Iron, Dehydrated nickel chloride, anhydrous stannic chloride, anhydrous stannous chloride, waterless cobaltous chloride, germanium chloride, beryllium chloride, zinc chloride and chlorination
It is cuprous.
As further preferably, the metal chloride is 1 with the mol ratio of thiophene-type sulfide:1—20:1.
As further preferred, the step 1) in, during the stirring, fuel oil is with the temperature of metal chloride
15—50℃。
As further preferred, the step 2) in, the solvent is selected from hydrochloric acid-aqueous solution, methanol-water solution and second
Alcohol-water solution.
As it is further preferably, the step 2) in, in the solvent, hydrochloric acid, methyl alcohol or ethanol are in aqueous
Mass fraction is 5-15wt%.
As it is further preferably, the step 2) in, during the dissolving, the thiophenic sulfur-metal chloride and solvent
Temperature be 5-100 DEG C.
As further preferred, the step 3) in, the purity of the thiophene-type sulfide for obtaining is 80-99%.
The beneficial effects of the invention are as follows：With fuel oil as raw material, preparation method includes thiophenic sulfur-metal chloride to the present invention
The step such as mixture generation, thiophene-type sulfide are separated with metal chloride, thiophene-type sulfide is refined, finally can from fuel oil
Extract the thiophene such as thiophene, monomethyl thiophene, thioxene, benzothiophene, monomethyl benzothiophene, dimethyl benzothiophene
Class sulfide, extraction efficiency is up to 99%, and the purity of thiophene-type sulfide product is 80-99%, and preparation method stabilization is practical.
Brief description of the drawings
Fig. 1 prepares the system schematic of thiophene-type sulfide for the embodiment of the present invention.
Description of symbols in accompanying drawing is as follows：It is continuous mixing kettle 1, solid-liquid separator 2, Liquid liquid Separation device 3, rectifying column 4, cold
Condenser 5, and reboiler 6.
Specific embodiment
The present invention overcomes and divides from fuel oil in the prior art by providing a kind of method for preparing thiophene-type sulfide
From the difficulty for extracting thiophenes sulfides.
Separation and Extraction goes out thiophene-type sulfide from consumer goods fuel oil, will there is good application prospect.But existing skill
In art, separation and Extraction goes out thiophenes sulfides not a duck soup from fuel oil.First, content of the thiophenes sulfides in fuel oil compared with
Low, sulfur content is generally measured with μ g/g.Next, the materialization of other components (such as aromatic hydrocarbons, alkene) in thiophenes sulfides and fuel oil
Property is approached, and aromatic hydrocarbons, alkene etc. have content very high (>10wt%).Furthermore, the thiophenes sulfides species in fuel oil is numerous
It is many, complicated components.These unfavorable factors cause that separation and Extraction process need to have sulphur selectivity higher, and thiophenic sulfur regenerating easily
Reclaim, this separation and extraction technology for resulting in current routine is difficult to effectively application.Traditional adsorption technology, using conventional activity
Charcoal, zeolite, activated alumina etc. are used as adsorbent, it is difficult to thiophenes sulfides are efficiently separated from oil.Using loaded metal ion
(such as Ce4+、Ni2+、Cu+Deng) adsorbent of molecular sieve, thiophenic sulfur can be separated from oil, using organic solvent washing adsorbent come
Regeneration thiophenic sulfur.However, though the pattern is with good fuel desulfuration effect, it is difficult to vulcanize for separation and Extraction thiophene
Thing.Firstly, since sorbent used very strong with thiophenic sulfur chemical action so that the regeneration of thiophenic sulfur needs to use substantial amounts of organic
Solvent washs adsorbent, and not only production cost is high, and the regeneration efficiency of thiophenic sulfur is also very low.Furthermore, organic solvent it is a large amount of
Using can also produce many volatile organic matters, cause the problem of secondary pollution.Traditional abstraction technique is also difficult to use in thiophene
The separation and Extraction of sulfide.First, considerable extractant can not efficiently separate thiophenic sulfur from oil.Furthermore, part is effectively
Extractant, expensive, thiophene sulfur regeneration is difficult.So far, there is no thiophene in the separation and Extraction fuel oil of complete set
The technology of class sulfide.
In order to solve drawbacks described above, the main thought of the embodiment of the present invention is：
The method that the embodiment of the present invention prepares thiophene-type sulfide, methods described comprises the following steps：
1) fuel oil is mixed with metal chloride stirring, reaction generation thiophenic sulfur-metal chloride suspension will be described
Solid-liquid suspension is separated off fuel oil, obtains thiophenic sulfur-metal chloride；
2) solvent of dissolving metal chloride is added in the thiophenic sulfur-metal chloride, stirring is obtained containing thiophene-based
The oil phase of sulfide and the water phase containing metal chloride, and by the oil phase and the aqueous phase separation；
3) oil phase containing thiophene-type sulfide is carried out into rectifying, obtains thiophene-type sulfide.
The fuel oil is mainly oil product of the boiling range below 350 DEG C, including gasoline, aviation kerosine, vacuum gas oil etc.；
The thiophene-type sulfide of fuel oil mainly includes that thiophenes sulfides include thiophene, monomethyl thiophene, thioxene, benzo thiophene
Fen, monomethyl benzothiophene, dimethyl benzothiophene etc.；Metal chloride used mainly includes anhydrous Aluminum chloride, anhydrous chlorination
Iron, anhydrous frerrous chloride, Dehydrated nickel chloride, anhydrous stannic chloride, anhydrous stannous chloride, waterless cobaltous chloride, germanium chloride, chlorination
Beryllium, zinc chloride, stannous chloride etc.；
The step 1) in, under stirring, there is chemistry in the thiophene-type sulfide in fuel oil with metal chloride
Reaction, thiophenic sulfur-metallic chloride mixture of the generation insoluble in oil, mixture also contains the component in some fuel oil,
And the state of suspension is presented in oil phase；The temperature of stirring is preferably 15-50 DEG C, to reach optimal reaction effect；The gold
The mol ratio of the thiophene-type sulfide in category chloride and fuel oil is 1:1—20:1.
The solvent is selected from hydrochloric acid-aqueous solution, methanol-water solution and ethanol-water solution etc..The step 2) in, stirring
Mix under state, thiophenic sulfur-metallic chloride mixture chemically reacts with solvent, thiophenic sulfur-metallic chloride mixture it
Between chemical action destroyed by solvent, and metal chloride is dissolved in solvent；Thiophenic sulfur-metallic chloride mixture with it is molten
The chemical reaction of agent is exothermic reaction, it is therefore desirable to have cooling water as cooling medium, with controlling reaction temperature 100 DEG C with
Under, prevent the aqueous solution from seething with excitement；After the operation such as agitated, liquid-liquid diphase can be formed, one is mutually the oil phase rich in thiophene-type sulfide,
Another phase is the water-soluble liquid phase containing metal chloride.Then, two-phase liquid is entered into Liquid liquid Separation device, separated operation, can
Realize that the oil phase rich in thiophene-type sulfide is separated with water-soluble liquid phase；Liquid liquid Separation device used includes gravity separator, eddy flow
Separator etc..
The step 3) in, the oil phase rich in thiophene-type sulfide is entered into rectifying column, carries out normal pressure continuous rectification behaviour
Make, after the vaporization of many second part and the process of partial condensation, different thiophenes sulfides and other fuel components, according to each waving
The difference of hair degree, can be collected in the corresponding height position of rectifying column；Distillation operation has also needed tower bottom reboiler and overhead condensation
Device, reboiler can provide a certain amount of upflowing vapor stream, and condenser can ensure there is suitable liquid-phase reflux；Have in rectifying column used
Column plate, or fill the filler of certain altitude；The cold medium of condenser used is cooling water, and cooling water temperature is 15-30 DEG C；Institute
With the thermal source of reboiler including steam, heat smoke, deep fat etc., heat source temperature is at 150-400 DEG C.
Finally obtained all kinds of thiophenes sulfides, thiophene, monomethyl thiophene, thioxene, benzothiophene, monomethyl benzo
The purity of the products such as thiophene, dimethyl benzothiophene is 80-99%.
In order to above and other purpose, feature and the advantage of the present invention can be become apparent, number cited below particularly is implemented
Example illustrates the method for preparing thiophene-type sulfide of the present invention.
Embodiment 1
As shown in figure 1, the process system that the embodiment of the present invention 1 prepares thiophene-type sulfide includes six kinds of capital equipments,
They are respectively continuous mixing kettle 1, solid-liquid separator 2, Liquid liquid Separation device 3, rectifying column 4, condenser 5, and reboiler 6.
These equipment form the three subsystems of the process system of the embodiment of the present invention 1：Thiophenic sulfur-metallic chloride mixture generation system
System, thiophene-type sulfide and metal chloride piece-rate system, thiophene-type sulfide refining system.
In thiophenic sulfur-metallic chloride mixture generation system, fuel oil enters with metal chloride anhydrous Aluminum chloride
In continuous mixing kettle 1, stirred at normal pressure and 15 DEG C, make the thiophene-type sulfide and anhydrous Aluminum chloride in fuel oil
Reaction is learned, thiophenic sulfur-metallic chloride mixture is generated.Sulfur content in fuel oil is 10000 μ g/g, metal chloride and thiophene
The mol ratio of class sulfide is 20:1, the volume of continuous mixing kettle is 100m3.Through the operation of solid-liquid separator 2, combustion is capable of achieving
Material oil is separated with thiophenic sulfur-metallic chloride mixture.Fuel oil yield is 70%.Solid-liquid separator used 2 is centrifuge.
In thiophene-type sulfide and metal chloride piece-rate system, thiophenic sulfur-metallic chloride mixture enters into another
In individual continuous mixing kettle 1, while hydrochloric acid-aqueous solution is also added in the stirred tank, stir at ambient pressure, thiophenic sulfur-metal
Chloride mix chemically reacts with hydrochloric acid-aqueous solution, and metal chloride is dissolved by hydrochloric acid-aqueous solution.Continous way is stirred
Mixing kettle 1 need to have cooling water as cooling medium, and control temperature in the kettle is below 100 DEG C, while the temperature of cooling water is 15-30
℃.In agitated kettle after operation, the oil phase rich in thiophene-type sulfide, and the water-soluble liquid phase containing metal chloride are formed.Its
Middle hydrochloric acid mass fraction in aqueous is 15wt%.Two-phase liquid is entered into Liquid liquid Separation device 3, separated operation, can
Realize that the oil phase rich in thiophene-type sulfide is separated with water-soluble liquid phase.Mass fraction of the thiophene-type sulfide in oil phase be
15wt%.Liquid liquid Separation device 3 used is gravity separator.
In thiophene-type sulfide refining system, the oil phase rich in thiophene-type sulfide is entered into rectifying column 4, carries out normal pressure
Continuous rectification is operated, and each thiophene-type sulfide sterling is collected in the corresponding height position of rectifying column.Distillation operation has also needed tower
Top condenser 5 and tower bottom reboiler 6.The cold medium of condenser used is cooling water, and cooling water temperature is 25-30 DEG C；It is used again
The thermal source of device is boiled including steam, heat smoke, deep fat etc., and heat source temperature is at 300-400 DEG C.Obtain all kinds of thiophenes sulfides products
Purity 80%.
Embodiment 2
As shown in figure 1, in thiophenic sulfur-metallic chloride mixture generation system, fuel oil is anhydrous with metal chloride
Iron chloride enters in continuous mixing kettle 1, is stirred at normal pressure and 50 DEG C, makes the thiophene-type sulfide and anhydrous chlorine in fuel oil
Change iron to chemically react, generate thiophenic sulfur-metallic chloride mixture.Sulfur content in fuel oil is 7000 μ g/g, metal chlorine
Compound is 15 with the mol ratio of thiophene-type sulfide:1, the volume of continuous mixing kettle is 100m3.Through the behaviour of solid-liquid separator 2
Make, be capable of achieving fuel oil and separated with thiophenic sulfur-metallic chloride mixture.Fuel oil yield is 82%.Separation of solid and liquid used
Device 2 is decanter.
In thiophene-type sulfide and metal chloride piece-rate system, thiophenic sulfur-metallic chloride mixture enters into another
In individual continuous mixing kettle 1, while methanol-water solution is also added in the stirred tank, stir at ambient pressure, thiophenic sulfur-metal
Chloride mix chemically reacts with methanol-water solution, and metal chloride is dissolved by methanol-water solution.Continous way is stirred
Mixing kettle 1 need to have cooling water as cooling medium, and control temperature in the kettle is below 100 DEG C, while the temperature of cooling water is 15-30
℃.In agitated kettle after operation, the oil phase rich in thiophene-type sulfide, and the water-soluble liquid phase containing metal chloride are formed.Its
Middle methyl alcohol mass fraction in aqueous is 5wt%.Two-phase liquid is entered into Liquid liquid Separation device 3, separated operation, can be real
Now the oil phase rich in thiophene-type sulfide is separated with water-soluble liquid phase.Mass fraction of the thiophene-type sulfide in oil phase be
20wt%.Liquid liquid Separation device 3 used is cyclone separator.
In thiophene-type sulfide refining system, the oil phase rich in thiophene-type sulfide is entered into rectifying column 4, carries out normal pressure
Continuous rectification is operated, and each thiophene-type sulfide sterling is collected in the corresponding height position of rectifying column.Distillation operation has also needed tower
Top condenser 5 and tower bottom reboiler 6.The cold medium of condenser used is cooling water, and cooling water temperature is 25-30 DEG C；It is used again
The thermal source of device is boiled including steam, heat smoke, deep fat etc., and heat source temperature is at 300-400 DEG C.Obtain all kinds of thiophenes sulfides products
Purity 86%.
Embodiment 3
As shown in figure 1, in thiophenic sulfur-metallic chloride mixture generation system, fuel oil and metal chloride chlorination
In cuprous entrance continuous mixing kettle 1, stirred at normal pressure and 30 DEG C, make the thiophene-type sulfide and stannous chloride in fuel oil
Chemically react, generate thiophenic sulfur-metallic chloride mixture.Sulfur content in fuel oil is 2000 μ g/g, metal chloride
It is 10 with the mol ratio of thiophene-type sulfide:1, the volume of continuous mixing kettle is 50m3.Through the operation of solid-liquid separator 2, can
Realize that fuel oil is separated with thiophenic sulfur-metallic chloride mixture.Fuel oil yield is 96%.Solid-liquid separator used 2 is
From filter.
In thiophene-type sulfide and metal chloride piece-rate system, thiophenic sulfur-metallic chloride mixture enters into another
In individual continuous mixing kettle 1, while ethanol-water solution is also added in the stirred tank, stir at ambient pressure, thiophenic sulfur-metal
Chloride mix chemically reacts with ethanol-water solution, and metal chloride is dissolved by ethanol-water solution.Continous way is stirred
Mixing kettle 1 need to have cooling water as cooling medium, and control temperature in the kettle is below 100 DEG C, while the temperature of cooling water is 15-30
℃.In agitated kettle after operation, the oil phase rich in thiophene-type sulfide, and the water-soluble liquid phase containing metal chloride are formed.Its
Middle ethanol mass fraction in aqueous is 10wt%.Two-phase liquid is entered into Liquid liquid Separation device 3, separated operation, can
Realize that the oil phase rich in thiophene-type sulfide is separated with water-soluble liquid phase.Mass fraction of the thiophene-type sulfide in oil phase be
23wt%.
In thiophene-type sulfide refining system, the oil phase rich in thiophene-type sulfide is entered into rectifying column 4, carries out normal pressure
Continuous rectification is operated, and each thiophene-type sulfide sterling is collected in the corresponding height position of rectifying column.Distillation operation has also needed tower
Top condenser 5 and tower bottom reboiler 6.The cold medium of condenser used is cooling water, and cooling water temperature is 25-30 DEG C；It is used again
The thermal source of device is boiled including steam, heat smoke, deep fat etc., and heat source temperature is at 300-400 DEG C.Obtain all kinds of thiophenes sulfides products
Purity 95%.
Embodiment 4
As shown in figure 1, in thiophenic sulfur-metallic chloride mixture generation system, fuel oil is anhydrous with metal chloride
Butter of tin enters in continuous mixing kettle 1, is stirred at normal pressure and 40 DEG C, make thiophene-type sulfide in fuel oil with it is anhydrous
Butter of tin chemically reacts, and generates thiophenic sulfur-metallic chloride mixture.Sulfur content in fuel oil is 1000 μ g/g, gold
Category chloride is 5 with the mol ratio of thiophene-type sulfide:1, the volume of continuous mixing kettle is 20m3.Through solid-liquid separator 2
Operation, is capable of achieving fuel oil and is separated with thiophenic sulfur-metallic chloride mixture.Fuel oil yield is 99%.
In thiophene-type sulfide and metal chloride piece-rate system, thiophenic sulfur-metallic chloride mixture enters into another
In individual continuous mixing kettle 1, while ethanol-water solution is also added in the stirred tank, stir at ambient pressure, thiophenic sulfur-metal
Chloride mix chemically reacts with ethanol-water solution, and metal chloride is dissolved by methanol-water solution.Continous way is stirred
Mixing kettle 1 need to have cooling water as cooling medium, and control temperature in the kettle is below 100 DEG C, while the temperature of cooling water is 15-30
℃.In agitated kettle after operation, the oil phase rich in thiophene-type sulfide, and the water-soluble liquid phase containing metal chloride are formed.Its
Middle methyl alcohol mass fraction in aqueous is 15wt%.Two-phase liquid is entered into Liquid liquid Separation device 3, separated operation, can
Realize that the oil phase rich in thiophene-type sulfide is separated with water-soluble liquid phase.Mass fraction of the thiophene-type sulfide in oil phase be
46wt%.
In thiophene-type sulfide refining system, the oil phase rich in thiophene-type sulfide is entered into rectifying column 4, carries out normal pressure
Continuous rectification is operated, and each thiophene-type sulfide sterling is collected in the corresponding height position of rectifying column.Distillation operation has also needed tower
Top condenser 5 and tower bottom reboiler 6.The cold medium of condenser used is cooling water, and cooling water temperature is 25-30 DEG C；It is used again
The thermal source of device is boiled including steam, heat smoke, deep fat etc., and heat source temperature is at 300-400 DEG C.Obtain all kinds of thiophenes sulfides products
Purity 99%.
Embodiment 5
As shown in figure 1, in thiophenic sulfur-metallic chloride mixture generation system, fuel oil and metal chloride chlorination
Beryllium enters in continuous mixing kettle 1, is stirred at normal pressure and 20 DEG C, the thiophene-type sulfide in fuel oil is occurred with beryllium chloride
Chemical reaction, generates thiophenic sulfur-metallic chloride mixture.Sulfur content in fuel oil is 300 μ g/g, metal chloride and thiophene
The mol ratio of class sulfide is 1:1, the volume of continuous mixing kettle is 50m3.Through the operation of solid-liquid separator 2, fuel is capable of achieving
Oil is separated with thiophenic sulfur-metallic chloride mixture.Fuel oil yield is 99%.
In thiophene-type sulfide and metal chloride piece-rate system, thiophenic sulfur-metallic chloride mixture enters into another
In individual continuous mixing kettle 1, while hydrochloric acid-aqueous solution is also added in the stirred tank, stir at ambient pressure, thiophenic sulfur-metal
Chloride mix chemically reacts with hydrochloric acid-aqueous solution, and metal chloride is dissolved by hydrochloric acid-aqueous solution.Continous way is stirred
Mixing kettle 1 need to have cooling water as cooling medium, and control temperature in the kettle is below 100 DEG C, while the temperature of cooling water is 15-30
℃.In agitated kettle after operation, the oil phase rich in thiophene-type sulfide, and the water-soluble liquid phase containing metal chloride are formed.Its
Middle hydrochloric acid mass fraction in aqueous is 10wt%.Two-phase liquid is entered into Liquid liquid Separation device 3, separated operation, can
Realize that the oil phase rich in thiophene-type sulfide is separated with water-soluble liquid phase.Mass fraction of the thiophene-type sulfide in oil phase be
14wt%.
In thiophene-type sulfide refining system, the oil phase rich in thiophene-type sulfide is entered into rectifying column 4, carries out normal pressure
Continuous rectification is operated, and each thiophene-type sulfide sterling is collected in the corresponding height position of rectifying column.Distillation operation has also needed tower
Top condenser 5 and tower bottom reboiler 6.The cold medium of condenser used is cooling water, and cooling water temperature is 15-25 DEG C；It is used again
The thermal source of device is boiled including steam, heat smoke, deep fat etc., and heat source temperature is at 150-300 DEG C.Obtain all kinds of thiophenes sulfides products
Purity 99%.
Technical scheme in above-mentioned the embodiment of the present application, at least has the following technical effect that or advantage：
With fuel oil as raw material, preparation method includes thiophenic sulfur-metallic chloride mixture generation, thiophene sulphur to the present invention
The step such as compound is separated with metal chloride, thiophene-type sulfide is refined, finally can extract out thiophene, monomethyl thiophene from fuel oil
The thiophene-type sulfides such as fen, thioxene, benzothiophene, monomethyl benzothiophene, dimethyl benzothiophene, extraction efficiency is high
Up to 99%, the purity of thiophene-type sulfide product is 80-99%, and preparation method stabilization is practical.
, but those skilled in the art once know basic creation although preferred embodiments of the present invention have been described
Property concept, then can make other change and modification to these embodiments.So, appended claims are intended to be construed to include excellent
Select embodiment and fall into having altered and changing for the scope of the invention.Obviously, those skilled in the art can be to the present invention
Carry out various changes and modification without departing from the spirit and scope of the present invention.So, if these modifications of the invention and modification
Belong within the scope of the claims in the present invention and its equivalent technologies, then the present invention is also intended to exist comprising these changes and modification
It is interior.
Claims (10)
1. a kind of method for preparing thiophene-type sulfide, it is characterised in that：Methods described comprises the following steps：
1) fuel oil is mixed with metal chloride stirring, reaction generation thiophenic sulfur-metal chloride suspension, by the suspension
Liquid separation of solid and liquid removes fuel oil, obtains thiophenic sulfur-metal chloride；
2) solvent of dissolving metal chloride is added in the thiophenic sulfur-metal chloride, stirring obtains vulcanizing containing thiophene-based
The oil phase of thing and the water phase containing metal chloride, and by the oil phase and the aqueous phase separation；
3) oil phase containing thiophene-type sulfide is carried out into rectifying, obtains thiophene-type sulfide.
2. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The fuel oil is selected from boiling range
It is 70 DEG C-350 DEG C of oil product, the sulfur content in the fuel oil is 100-10000 μ g/g.
3. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The thiophene-type sulfide choosing
From thiophene, monomethyl thiophene, thioxene, benzothiophene, monomethyl benzothiophene and dimethyl benzothiophene.
4. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The metal chloride is selected from
It is anhydrous Aluminum chloride, anhydrous ferric chloride, anhydrous frerrous chloride, Dehydrated nickel chloride, anhydrous stannic chloride, anhydrous stannous chloride, anhydrous
Cobalt chloride, germanium chloride, beryllium chloride, zinc chloride and stannous chloride.
5. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The metal chloride and thiophene
The mol ratio of fen class sulfide is 1:1—20:1.
6. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The step 1) in, it is described
During stirring, fuel oil is 15-50 DEG C with the temperature of metal chloride.
7. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The step 2) in, it is described
Solvent is selected from hydrochloric acid-aqueous solution, methanol-water solution and ethanol-water solution.
8. the method for preparing thiophene-type sulfide according to claim 7, it is characterised in that：The step 2) in, it is described
In solvent, hydrochloric acid, methyl alcohol or ethanol mass fraction in aqueous are 5-15wt%.
9. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The step 2) in, it is described
During dissolving, the temperature of the thiophenic sulfur-metal chloride and solvent is 5-100 DEG C.
10. the method for preparing thiophene-type sulfide according to claim 1, it is characterised in that：The step 3) in, obtain
The thiophene-type sulfide purity be 80-99%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735854A (en) * | 2008-11-20 | 2010-06-16 | 通用电气公司 | Method and system for removing impurites from hydrocarbon oils via lewis acid complexation |
| CN102977911A (en) * | 2012-12-05 | 2013-03-20 | 北京化工大学 | Method for removing thiophene sulfides in fuel oil by catalytic oxidation extraction |
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2017
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735854A (en) * | 2008-11-20 | 2010-06-16 | 通用电气公司 | Method and system for removing impurites from hydrocarbon oils via lewis acid complexation |
| CN102977911A (en) * | 2012-12-05 | 2013-03-20 | 北京化工大学 | Method for removing thiophene sulfides in fuel oil by catalytic oxidation extraction |
Non-Patent Citations (1)
| Title |
|---|
| JIA-JUN GAO等: "Removal Mechanism of Thiophenic Compounds in Model Oil by Inorganic Lewis Acids", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
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