CN106215844A - The adsorbent of a kind of sulfide for removing in organic solvent and method - Google Patents
The adsorbent of a kind of sulfide for removing in organic solvent and method Download PDFInfo
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- CN106215844A CN106215844A CN201610634331.XA CN201610634331A CN106215844A CN 106215844 A CN106215844 A CN 106215844A CN 201610634331 A CN201610634331 A CN 201610634331A CN 106215844 A CN106215844 A CN 106215844A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
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Abstract
The present invention relates to the adsorbent of a kind of sulfide for removing in organic solvent, it is by copper compound powder and/or silver compound powder constituent, and the particle diameter of described copper compound powder and/or silver compound powder is 0.1 μm 100 μm.A kind of method that present invention also offers sulfide for removing in organic solvent, comprises the following steps: 1) adsorbent according to any one of claim 13 is added in described organic solvent；2) stirring；3) described adsorbent is separated with described organic solvent.The desulfurizing agent that the present invention uses is non-loading type desulfurizing agent, directly uses copper compound powder and/or silver compound powder to prepare, and preparation is simple, low cost.The adsorbent of the application of the invention and sulfur method, effectively can take out sulfide from organic solvent, sulfur content therein be reduced to below 10ppmw, and adsorbent Sulfur capacity is higher than traditional load type adsorbing agent.
Description
Technical field
The present invention relates to petrochemical industry, more specifically it relates to a kind of gasoline desulfurizer and sulfur method.
Background technology
Along with environmental law is increasingly stricter to the restriction of the discharge of sulfur content, the most effectively remove in the fuel oil such as gasoline
Sulfur-containing compound attract the extensive concern of people always.China starts to carry out in urban from December in 2013 on the 18th
" state V " standard, it is contemplated that " state V (≤10ppmw) " standard was carried out in the whole nation from 1 day January in 2018.Traditional hydrodesulfurization side
Method, can remove some simple sulfur-containing compounds effectively, such as mercaptan, thioether etc., the complex compound removed for some difficulties
The removing of (such as benzothiophene, dibenzothiophenes and derivant thereof) often leads to a large amount of losses of octane number, and operating cost ratio
Higher, condition is harsh, reacts under conditions of needing at high temperature such as 300 DEG C and add pressure, and hydrogen participation.Later
Researchers devise some new methods for the sulfur-containing compound removing in fuel oil, such as abstraction desulfurization, absorption desulfurization,
Microbial degradation desulfurization etc..Wherein, absorption desulfurization participates in owing to operating condition is gentle, can reach deep desulfuration, need not hydrogen
Researcher keen interest is attract etc. advantage.Absorption desulfurization mainly uses load type adsorbing agent to realize the purpose of desulfurization, phase
For traditional Hydrobon catalyst, it is more convenient that load type adsorbing agent has use, can reach the advantages such as deep desulfuration, but its
Preparation section is cumbersome, and is difficult to regenerate, and active component easily runs off, and aperture utilization rate is the highest, thus improves infusion of financial resources.
Patent CN105126747 discloses the preparation method of a kind of cupric mesoporous adsorbent for gasoline desulfurization, by hydrothermal crystallization method
Combine with pH regulator method, the mesoporous SBA-15 molecular sieve of the copper load of synthesis high dispersive, then by room temperature low concentration hydrazine hydrate
Prepare the mesoporous SBA-15 molecular sieve containing the load of monovalence copper.Use this adsorbent that thiophene compound in analog gasoline is inhaled
Time attached, the degree of depth of purification is not enough (500mg/L is down to 404mg/L), and sulfur capacity the highest (7.31mg S/g adsorbent), adsorbent
Prepare relatively cumbersome；Patent CN101327421 discloses the preparation side of a kind of load type adsorbing agent for petroleum fraction desulfuration
Method, first prepares aluminium sesquioxide powder body by sol-gel process, is then roughened and activates sensitized treatment, use electroless plating method afterwards
In powder surface copper facing, prepare load type adsorbing agent.This adsorbent can reach in the Staticadsorption experiment to mercaptan
The removal efficiency of 99.61%, but its preparation section is cumbersome；Patent CN102000544 discloses a kind of suction for gasoline desulfurization
Attached dose and preparation method thereof and application in gasoline desulfurization, this adsorbent is by Cu-lyt. and the doped meso-porous oxidation of aluminium element
Si molecular sieves after being fully ground, roasting prepares under an inert atmosphere, and this adsorbent utilizes absorption method, to thiophene in analog gasoline
Compound (concentration is 500ppm) removing has preferable effect, but adsorbs Sulfur capacity the highest (7.36mg S/g)；
Summary of the invention
In order to eliminate, some load type adsorbing agents are the highest to aperture utilization rate, active component is easy to run off, preparation section is more multiple
Miscellaneous, the shortcomings such as adsorbent sulfur capacity is low, the invention provides the adsorbent of a kind of sulfide for removing in organic solvent, its
It is characterised by, by copper compound powder and/or silver compound powder constituent, described copper compound powder and/or silver compound powder
The particle diameter at end is 0.1 μm-100 μm.
Further, described copper compound be Red copper oxide, Hydro-Giene (Water Science)., Cu-lyt., copper fluoride, cuprous sulfide,
Cupricin., cuprous acetate, cuprous sulfate, oxalic acid are cuprous, phosphoric acid is cuprous or its mixture.
Further, described silver compound is silver oxide, Silver monobromide, silver iodide, silver nitrate, silver chloride, Argentous sulfide., sulphuric acid
Silver, silver oxalate, silver phosphate or its mixture.
A kind of method that the invention also discloses sulfide for removing in organic solvent, comprises the following steps:
1) described adsorbent is added in described organic solvent；
2) stirring；
3) described adsorbent is separated with described organic solvent.
Preferably, described organic solvent is the gases such as ethylene, propylene, butane, hexamethylene, cyclohexene or its mixture；Liquid
The liquid such as liquefied oil gas, gasoline, kerosene, diesel oil, machine oil or its mixture.
Preferably, described sulfide is hydrogen sulfide, Carbon bisulfide, mercaptan, thioether, thiophene and derivatives, benzothiophene
Or derivatives thereof, dibenzothiophenes or derivatives thereof.
Preferably, the institute of described method is the most all carried out at 20-70 DEG C.
Preferably, step 2) in mixing time be 0.5-10 hour.
Preferably, said method comprising the steps of:
1) described adsorbent is added in described organic solvent；
2) stir 0.5-10 hour at 20-70 DEG C；
3) described adsorbent is separated with described organic solvent.
The desulfurizing agent that the present invention uses is non-loading type desulfurizing agent, directly uses copper compound powder and/or silver compound
Prepared by powder, preparation is simple, low cost.The adsorbent of the application of the invention and sulfur method, can be effectively from organic solvent
Middle taking-up sulfide, is reduced to sulfur content therein below 10ppmw, and adsorbent Sulfur capacity is higher than traditional support type absorption
Agent.
Detailed description of the invention
Being described principle and the feature of the present invention below in conjunction with example, example is served only for explaining the present invention, and
Non-for limiting the scope of the present invention.
Embodiment 1
Weigh the Cu-lyt. powder that 0.058g particle diameter is 0.1 μm-100 μm, join 100ml and contain 80ppmw thiophene
In cyclohexane solution, under the conditions of normal pressure and 20 DEG C, stirring and adsorbing five hours, with micro-coulometric titration instrument to the hexamethylene after desulfurization
Alkane is sampled analyzing.Cu-lyt. adsorbent Sulfur capacity is 121.59mg S/g adsorbent, remains thiophene solution sulfur in hexamethylene
Content is 9.48ppmw.
Embodiment 2
Weigh the silver chloride powder that 0.055g particle diameter is 0.1 μm-100 μm, join 100ml and contain the ring of 80ppmw thiophene
In hexane solution, under the conditions of normal pressure and 40 DEG C, stirring and adsorbing five hours, with micro-coulometric titration instrument to the hexamethylene after desulfurization
It is sampled analyzing.Silver chloride adsorbent Sulfur capacity is 133.75mg S/g adsorbent, remains thiophene solution sulfur content in hexamethylene
For 6.44ppmw.
Embodiment 3
Weighing the cuprous acetate powder that 0.020g particle diameter is 0.1 μm-100 μm respectively, 0.030g particle diameter is 0.1 μm-100 μm
Silver chloride powder, join in the normal octane solution that 100ml contains 70ppmw benzothiophene, under the conditions of normal pressure and 70 DEG C,
Stirring and adsorbing five hours, is sampled analyzing to the hexamethylene after desulfurization with micro-coulometric titration instrument.The maximum Sulfur capacity of mixture
For 124.88mg S/g adsorbent, remaining benzothiophene solution sulfur content in normal octane is 7.56ppmw.
Embodiment 4
Weighing the Cu-lyt. powder that 0.030g particle diameter is 0.1 μm-100 μm respectively, 0.020g particle diameter is 0.1 μm-100 μm
Silver phosphate powder, join in the gasoline solution that 100ml contains 70ppmw ethyl mercaptan, under the conditions of normal pressure and 50 DEG C, stirring
Adsorb five hours, be sampled analyzing to the gasoline after desulfurization with micro-coulometric titration instrument.The maximum Sulfur capacity of mixture is
124.18mg S/g adsorbent, remaining ethyl mercaptan solution sulfur content in gasoline is 7.91ppmw.
Embodiment 5
Weighing the cuprous powder of oxalic acid that 0.030g particle diameter is 0.1 μm-100 μm respectively, 0.030g particle diameter is 0.1 μm-100 μm
Silver phosphate powder, join in the normal octane solution that 100ml contains 80ppmw thiophene, under the conditions of normal pressure and 70 DEG C, stirring
Adsorb five hours, be sampled analyzing to the normal octane after desulfurization with micro-coulometric titration instrument.The maximum Sulfur capacity of mixture is
122.28mg S/g adsorbent, remaining thiophene solution sulfur content in normal octane is 6.63ppmw.
Comparison example 1
Weigh the alumina adsorbant 0.300g that support type Cu-lyt. is active component prepared with equi-volume impregnating
(CuCl content is 10%m/m), joins in the cyclohexane solution that 100ml contains 90ppmw dibenzothiophenes, at normal pressure and 30
Under the conditions of DEG C, stirring and adsorbing five hours, it is sampled analyzing to the hexamethylene after desulfurization with micro-coulometric titration instrument.Support type chlorine
The maximum Sulfur capacity changing cuprous/alumina adsorbant is 15.11mg S/g adsorbent, remains dibenzothiophenes solution sulfur in hexamethylene
Content is 44.69ppmw.
Comparison example 2
Weigh the alumina adsorbant 0.150g that support type silver nitrate is active component prepared with equi-volume impregnating
(AgNO3Content is 12%m/m), join in the normal octane solution that 100ml contains 80ppmw ethyl mercaptan, at normal pressure and 20 DEG C of bars
Under part, stirring and adsorbing five hours, it is sampled analyzing to the normal octane after desulfurization with micro-coulometric titration instrument.Support type nitric acid
The maximum Sulfur capacity of silver/alumina adsorbant is 25.78mg S/g adsorbent, remains ethyl mercaptan solution sulfur content and be in normal octane
41.33ppmw。
Comparison example 3
Weigh the silicon oxide that Cu-lyt. support type Cu-lyt. the is active component absorption prepared with equi-volume impregnating
Agent 0.300g (CuCl content is 12%m/m), joins in the cyclohexane solution that 100ml contains 80ppmw thiophene, at normal pressure and
Under the conditions of 40 DEG C, stirring and adsorbing five hours, it is sampled analyzing to the hexamethylene after desulfurization with micro-coulometric titration instrument.Support type
The maximum Sulfur capacity of Cu-lyt ./alumina adsorbant is 11.22mg S/g adsorbent, remains thiophene solution sulfur content in hexamethylene
For 46.34ppmw.
Comparison example 4
Weigh the acticarbon 0.300g that support type Cu-lyt. is active component prepared with equi-volume impregnating
(CuCl content is 12%m/m), joins in the gasoline solution that 100ml contains 80ppmw thiophene, under the conditions of normal pressure and 60 DEG C,
Stirring and adsorbing five hours, is sampled analyzing to the gasoline after desulfurization with micro-coulometric titration instrument.Support type Cu-lyt ./activity
The maximum Sulfur capacity of carbon adsorbent is 9.54mg S/g adsorbent, and remaining thiophene solution sulfur content in gasoline is 51.37ppmw.
Compared with comparison example 1-4, use adsorbent and the sulfur method of embodiment 1-5, can more effectively remove sulfur-bearing
Sulfide in organic solvent, is remained far below by traditional load by the sulfide in the organic solvent that the method processes
The organic solvent of type sorbent treatment.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all spirit in the present invention and
Within principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. the adsorbent being used for removing the sulfide in organic solvent, it is characterised in that by copper compound powder and/or silver
Compound powder forms, and the particle diameter of described copper compound powder and/or silver compound powder is 0.1 μm-100 μm.
Adsorbent the most according to claim 1, it is characterised in that described copper compound is Red copper oxide, Hydro-Giene (Water Science)., chlorine
Change cuprous, copper fluoride, cuprous sulfide, Cupricin., cuprous acetate, cuprous sulfate, oxalic acid are cuprous, phosphoric acid is cuprous or its mixing
Thing.
Adsorbent the most according to claim 1, it is characterised in that described silver compound is silver oxide, Silver monobromide, iodate
Silver, silver nitrate, silver chloride, Argentous sulfide., silver sulfate, silver oxalate, silver phosphate or its mixture.
4. the method being used for removing the sulfide in organic solvent, it is characterised in that comprise the following steps:
1) adsorbent according to any one of claim 1-3 is added in the organic solvent containing sulfide；
2) stirring；
3) described adsorbent is separated with described organic solvent.
Method the most according to claim 4, it is characterised in that described organic solvent be ethylene, propylene, butane, hexamethylene,
Cyclohexene or its mixture.
Method the most according to claim 4, it is characterised in that described organic solvent be liquefied petroleum gas, gasoline, kerosene,
Diesel oil, machine oil or its mixture.
Method the most according to claim 4, it is characterised in that described sulfide is hydrogen sulfide, Carbon bisulfide, mercaptan, sulfur
Ether, thiophene and derivatives, benzothiophene or derivatives thereof, dibenzothiophenes or derivatives thereof.
Method the most according to claim 4, it is characterised in that the institute of described method is the most all carried out at 20-70 DEG C.
Method the most according to claim 4, it is characterised in that step 2) in stirring time be 0.5-10 hour.
Method the most according to claim 4, it is characterised in that said method comprising the steps of:
1) described adsorbent is added in the organic solvent containing sulfide；
2) stir 0.5-10 hour at 20-70 DEG C；
3) described adsorbent is separated with described organic solvent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078583A (en) * | 2019-06-06 | 2019-08-02 | 太仓沪试试剂有限公司 | A kind of purification process of iodoethane |
| CN110523370A (en) * | 2019-08-14 | 2019-12-03 | 华南理工大学 | A kind of room temperature removes the adsorbent and its method of benzyldithio toluene in transformer oil |
| CN111778062A (en) * | 2020-06-16 | 2020-10-16 | 泰州九润环保科技有限公司 | Method for deep adsorption desulfurization of oil by using metal/mesoporous organic silicon oxide nanotube |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041764A (en) * | 2012-12-24 | 2013-04-17 | 南京工业大学 | Adsorbent for desulfurization of fuel oil, preparation method and application thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041764A (en) * | 2012-12-24 | 2013-04-17 | 南京工业大学 | Adsorbent for desulfurization of fuel oil, preparation method and application thereof |
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| 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110078583A (en) * | 2019-06-06 | 2019-08-02 | 太仓沪试试剂有限公司 | A kind of purification process of iodoethane |
| CN110523370A (en) * | 2019-08-14 | 2019-12-03 | 华南理工大学 | A kind of room temperature removes the adsorbent and its method of benzyldithio toluene in transformer oil |
| CN110523370B (en) * | 2019-08-14 | 2021-12-17 | 华南理工大学 | Adsorbent for removing dibenzyl disulfide from transformer oil at normal temperature and method thereof |
| CN111778062A (en) * | 2020-06-16 | 2020-10-16 | 泰州九润环保科技有限公司 | Method for deep adsorption desulfurization of oil by using metal/mesoporous organic silicon oxide nanotube |
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