CN106566577A - Method for removal of sulfide in oil product by molecular sieve catalytic oxidation - Google Patents
Method for removal of sulfide in oil product by molecular sieve catalytic oxidation Download PDFInfo
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- CN106566577A CN106566577A CN201510655569.6A CN201510655569A CN106566577A CN 106566577 A CN106566577 A CN 106566577A CN 201510655569 A CN201510655569 A CN 201510655569A CN 106566577 A CN106566577 A CN 106566577A
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- molecular sieve
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Abstract
The invention relates to a method for removal of sulfide in an oil product by molecular sieve catalytic oxidation, and mainly solves the problems of low sulfur saturation capacity of adsorbents and incomplete removal in the prior art. The method adopts the step of contacting an oil product, hydrogen peroxide and a molecular sieve. The molecular sieve is M-Ti-HMS, wherein M is an element selected from IB, IIB, IVB, VB, VIB, VIIB or VIII group except Ti, and in the molecular sieve, Si and M are in a mole ratio of 1-100. The technical scheme well solves the problem, and can be used in the industrial production for removal of sulfide in an oil product by molecular sieve catalytic oxidation.
Description
Technical field
The present invention relates in a kind of molecular sieve catalytic oxidation removal oil product sulfide method.
Background technology
HMS mesoporous materials are the mesoporous silicon materials of a class hexagonal phase structure, due to long-range order
And the unordered institutional framework of short distance, since the synthesis in the industries such as petrochemical industry grinding as catalyst
Send out and be subject to enough attention.In recent years, as countries in the world propose increasingly stricter sulfur-bearing standard,
How effective desulfurization, producing ultra-clean fuel oil becomes study hotspot both domestic and external and in the urgent need to address
Problem.Wherein, HTS receives more next as a kind of catalyst of efficient, environmental protection
More concerns.
With progressively going deep into for research work, it has been found that HMS materials are relative to M41S series materials
Material has thicker hole wall, higher hydrothermal stability and is more suitable for the framework modification advantage of material.
Therefore, in recent years the research of HMS materials becomes the important directions of mesoporous silicon material again.Particularly
With HMS materials as carrier, by metal or nonmetalloid, inorganic salts, organic macromolecule or life
Active substances etc. are modified its skeleton, duct, surface or modified etc. are more become new function
Change the study hotspot of material.At present, the heteroatom mesopore such as Ti, Zr, V, Cr, Mn, Cu and Fe
The synthesis of molecular sieve, characterize and catalytic performance research common report.But to heteroatom mesopore point
Son sieve catalysis behavior investigation more be confined to catalysis oxidation aspect, and it is most research concentrate on
HMS is carrier.Ti-HMS is used as a kind of excellent carrier, the research being modified to it at present
It is also less.Zepeda etc. and Halachev etc. with Ti-HMS as carrier, prepare respectively CoMo and
NiW bimetallic catalysts obtain preferable desulfurized effect for hydrodesulfurization reaction.Subsequently to grind
The removing for studying carefully macromolecular sulfide provides beneficial approach.
At present conventional sulfur method has hydrodesulfurization, catalytic desulfurization, rectifying desulfurization and absorption desulfurization.
Hydrodesulfurization is due to needing hydrogen source, and the phenyl ring of aromatic hydrocarbons can be hydrogenated in hydrodesulfurization, because
This high cost and aroamtic hydrocarbon raw material loss is serious, is not suitable for aromatizing and desulfurizing.Rectifying desulphurization plant is invested into
This height, and because some sulfide and aromatic hydrocarbons form common waste, desulfurization precision does not reach technological requirement.
The Sulfur capacity saturated capacity that absorption desulfurization has adsorbent is low, removes halfway problem.
CN101525549A discloses a kind of hydrocracking tail oil deep adsorbent desulfurizing and denitrifying method, and it includes
By hydrocracking tail oil and a kind of hydrocracking tail oil depth containing a certain amount of sulfide and nitride
Absorption desulfurization, denitrifier are contacted under uniform temperature, pressure and air speed, obtain adsorption refining
Desulfurization removing nitric hydrocracking tail oil afterwards, product sulphur nitrogen content meets hydroisomerizing dewaxed feedstock requirement.
But the method has that complex process, equipment investment and running cost are high, non-renewable.
The content of the invention
The technical problem to be solved is the Sulfur capacity saturated capacity that prior art has adsorbent
It is low, remove halfway problem, there is provided sulfide in a kind of molecular sieve catalytic oxidation removal oil product
Method.The method has the characteristics of absorption property is strong, and adsorption capacity is big.
To solve above-mentioned technical problem, the technical scheme that the present invention takes is as follows：A kind of molecular sieve is urged
The method for changing sulfide in oxidation removal oil product, contacts including oil product, hydrogen peroxide is made with molecular sieve
The step of；The molecular sieve be M-Ti-HMS, wherein, M be in addition to Ti selected from IB, IIB,
The element of IVB, VB, VI B, VII B or VIII race；In the molecular sieve, the mol ratio of Si and M
For 1～100.
In above-mentioned technical proposal, it is preferable that the mol ratio of Si and M is 10～70.It is highly preferred that
The mol ratio of Si and M is 10～60.
In above-mentioned technical proposal, it is preferable that the concentration of sulfide is 0.01～20000 milligram in oil product
/ kilogram.The concentration of sulfide is 0.1～8000 mg/kg more preferably in oil product.
In above-mentioned technical proposal, it is preferable that M selected from Cu, Ag, Au, Zn, Ti, Zr, V,
In Nb, Cr, Mo, W, Mn, Re, Fe, Co, Ni, Ru, Rh, Pd or Pt at least
It is a kind of.It is highly preferred that at least one of the M in Cu, Ag, Zn or Ni.
In above-mentioned technical proposal, it is preferable that the sulfide is thiophene, 2- methylthiophenes, 3- methyl
Thiophene, 2,5- thioxenes, 2,4- thioxenes, 2,3- thioxenes, 3,4- dimethyl thiophenes
Fen, tetramethyl thiophene, methyl mercaptan, ethyl mercaptan, propanethiol, isobutyl mercaptan, diethyl thioether,
At least one in cos or carbon disulfide.
In above-mentioned technical proposal, it is preferable that oil product is 0.1～10 hour with molecular sieve time of contact,
Oil product is 10～100 DEG C with molecular sieve Contact Temperature, and hydrogen peroxide is with the mol ratio of sulphur in oil product
3～6, the consumption of molecular sieve is the 1～3% of oil product weight.
In above-mentioned technical proposal, it is preferable that in the molecular sieve M-Ti-HMS, Si/Ti mol ratios
For 10～60.
Molecular sieve M-Ti-HMS described in the inventive method is with the metal-modified Ti-HMS containing M
Molecular sieve.Method of modifying is infusion process known in the art, in-situ synthesis or NH3The precipitation method.
By the present invention in that the oil product of sulfur-bearing, such as hydrocracking tail oil, in M-Ti-HMS molecules
In the presence of sieve, there is catalytic oxidation, effectively remove sulfide, the removal efficiency of sulfide
Can reach more than 90%.Simultaneously as removal efficiency is high so that the service cycle of adsorbent extends,
Corresponding production cost is reduced, and achieves preferable technique effect.
With reference to embodiment, the invention will be further elaborated.
Specific embodiment
【Embodiment 1】
With Ti-HMS as carrier (Si/Ti mol ratios are 20), with Cu (NO3)2For Cu sources, adopt
It is 10 dipping 5 hours according to Si/Cu mol ratios with infusion process, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Cu/Ti-HMS-10 samples, and 10 is Si/Cu mol ratios.
Thiophene, 2,5- thioxenes and ethyl mercaptan are dissolved in normal octane, thiophene content is
150mg/kg, 2,5- thioxene contents are 50mg/kg, and ethyl mercaptan content is 50mg/kg, is made
Obtain mould oil.
Weigh【Embodiment 1】In 0.1 gram of Cu/Ti-HMS-10 sample in conical flask, plus
Enter 10ml mould oils, acetonitrile as solvents treats the temperature stabilization of heat collecting type constant temperature blender with magnetic force to 70
DEG C, add 0.5gH in flask rapidly2O2(mass fraction is 30%), by flask water-bath is put into
In pot, reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined de-
Sulfur content after sulphur in oil phase.The removal efficiency of sulfide is 92.62%.
【Comparative example 1】
With HMS as carrier (Si/Ti mol ratios are 20), with Cu (NO3)2For Cu sources, adopt
Infusion process is 10 dipping 5 hours according to Si/Cu mol ratios, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Cu-HMS samples.
0.1 gram of Cu-HMS sample is weighed in conical flask, 10ml is added【Embodiment 1】In
Mould oil, acetonitrile as solvents, after heat collecting type constant temperature blender with magnetic force temperature stabilization to after 70 DEG C,
Add 0.5gH in flask rapidly2O2(mass fraction is 30%), flask is put in water-bath,
Reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined oil after desulfurization
Sulfur content in phase.The removal efficiency of sulfide is 86.87%.
【Embodiment 2】
With Ti-HMS as carrier (Si/Ti mol ratios are 25), with Cu (NO3)2For Cu sources, adopt
Impregnated 5 hours according to Si/Cu mol ratios 20 with infusion process, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Cu/Ti-HMS-20 samples.
0.2 gram of Cu/Ti-HMS-20 sample is weighed in conical flask, 10ml is added【Embodiment 1】
In mould oil, acetonitrile as solvents treats the temperature stabilization to 70 DEG C of heat collecting type constant temperature blender with magnetic force
Afterwards, in flask 0.5gH is added rapidly2O2(mass fraction is 30%), by flask water-bath is put into
In pot, reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined de-
Sulfur content after sulphur in oil phase.The removal efficiency of sulfide is 91.58%.
【Embodiment 3】
With Ti-HMS as carrier (Si/Ti mol ratios are 40), with Cu (NO3)2For Cu sources, adopt
Impregnated 5 hours according to Si/Cu mol ratios 30 with infusion process, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Cu/Ti-HMS-40 samples.
0.2 gram of Cu/Ti-HMS-40 sample is weighed in conical flask, 10ml is added【Embodiment 1】
In mould oil, acetonitrile as solvents treats the temperature stabilization to 70 DEG C of heat collecting type constant temperature blender with magnetic force
Afterwards, in flask 0.4gH is added rapidly2O2(mass fraction is 30%), by flask water-bath is put into
In pot, reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined de-
Sulfur content after sulphur in oil phase.The removal efficiency of sulfide is 88.42%.
【Embodiment 4】
With Ti-HMS as carrier (Si/Ti mol ratios are 60), with Cu (NO3)2For Cu sources, adopt
Impregnated 5 hours according to Si/Cu mol ratios 10 with infusion process, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Cu/Ti-HMS-60 samples.
0.1 gram of Cu/Ti-HMS-60 sample is weighed in conical flask, 10ml is added【Embodiment 1】
In mould oil, acetonitrile as solvents treats the temperature stabilization to 70 DEG C of heat collecting type constant temperature blender with magnetic force
Afterwards, in flask 0.3gH is added rapidly2O2(mass fraction is 30%), by flask water-bath is put into
In pot, reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined de-
Sulfur content after sulphur in oil phase.The removal efficiency of sulfide is 86.87%.
【Embodiment 5】
With Ti-HMS as carrier (Si/Ti mol ratios are 10), with AgNO3For Ag sources, adopt
Infusion process impregnates 5 hours according to Si/Ag mol ratios 15, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Ag/Ti-HMS-15 samples.
0.1 gram of Ag/Ti-HMS-15 sample is weighed in conical flask, 10ml is added【Embodiment 1】
In mould oil, acetonitrile as solvents treats the temperature stabilization to 70 DEG C of heat collecting type constant temperature blender with magnetic force
Afterwards, in flask 0.4gH is added rapidly2O2(mass fraction is 30%), by flask water-bath is put into
In pot, reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined de-
Sulfur content after sulphur in oil phase.The removal efficiency of sulfide is 90.21%.
【Comparative example 2】
With HMS as carrier (Si/Ti mol ratios are 10), with AgNO3For Ag sources, using leaching
Stain method impregnates 5 hours according to Si/Ag mol ratios 15, then 70 DEG C of dryings 5 hours, 550 DEG C of roastings
Burn 4 hours, obtain Ag-HMS samples.
0.1 gram of Ag-HMS sample is weighed in conical flask, 10ml is added【Embodiment 1】In
Mould oil, acetonitrile as solvents, after heat collecting type constant temperature blender with magnetic force temperature stabilization to after 70 DEG C,
Add 0.4gH in flask rapidly2O2(mass fraction is 30%), flask is put in water-bath,
Reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined oil after desulfurization
Sulfur content in phase.The removal efficiency of sulfide is 85.64%.
【Embodiment 6】
With Ti-HMS as carrier (Si/Ti mol ratios are 30), with Zn (NO3)2For Zn sources, adopt
Impregnated 5 hours according to Si/Zn mol ratios 25 with infusion process, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Zn/Ti-HMS-25 samples.
0.2 gram of Zn/Ti-HMS-25 sample is weighed in conical flask, 10ml is added【Embodiment 1】
In mould oil, acetonitrile as solvents treats the temperature stabilization to 70 DEG C of heat collecting type constant temperature blender with magnetic force
Afterwards, in flask 0.5gH is added rapidly2O2(mass fraction is 30%), by flask water-bath is put into
In pot, reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined de-
Sulfur content after sulphur in oil phase.The removal efficiency of sulfide is 89.46%.
【Comparative example 3】
With HMS as carrier (Si/Ti mol ratios are 30), with Zn (NO3)2For Zn sources, adopt
Infusion process impregnates 5 hours according to Si/Zn mol ratios 25, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Zn-HMS samples.
0.2 gram of Zn-HMS sample is weighed in conical flask, 10ml is added【Embodiment 1】In
Mould oil, acetonitrile as solvents, after heat collecting type constant temperature blender with magnetic force temperature stabilization to after 70 DEG C,
Add 0.5gH in flask rapidly2O2(mass fraction is 30%), flask is put in water-bath,
Reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined oil after desulfurization
Sulfur content in phase.The removal efficiency of sulfide is 78.53%.
【Embodiment 7】
With Ti-HMS as carrier (Si/Ti mol ratios are 10), with Ni (NO3)2For Ni sources, adopt
Impregnated 5 hours according to Si/Ni mol ratios 30 with infusion process, then 70 DEG C of dryings 5 hours, 550 DEG C
Roasting 4 hours, obtains Ni/Ti-HMS-30 samples.
0.1 gram of Ni/Ti-HMS-30 sample is weighed in conical flask, 10ml is added【Embodiment 1】
In mould oil, acetonitrile as solvents treats the temperature stabilization to 70 DEG C of heat collecting type constant temperature blender with magnetic force
Afterwards, in flask 0.4gH is added rapidly2O2(mass fraction is 30%), by flask water-bath is put into
In pot, reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined de-
Sulfur content after sulphur in oil phase.The removal efficiency of sulfide is 89.57%.
【Comparative example 4】
With HMS as carrier (Si/Ti mol ratios are 10), with Ni (NO3) 2 as Ni sources, adopt
Infusion process impregnates 5 hours according to Si/Ni mol ratios 30, then 70 DEG C of dryings 5 hours, 550 DEG C of roastings
Burn 4 hours, obtain Ni-HMS samples.
0.08 gram of Ni-HMS sample is weighed in conical flask, 10ml is added【Embodiment 1】In
Mould oil, acetonitrile as solvents, after heat collecting type constant temperature blender with magnetic force temperature stabilization to after 70 DEG C,
Add 0.3gH in flask rapidly2O2(mass fraction is 30%), flask is put in water-bath,
Reaction is finished and is cooled to after room temperature, uses electronic centrifuge, is taken supernatant liquor and is determined oil after desulfurization
Sulfur content in phase.The removal efficiency of sulfide is 77.45%.
Claims (10)
1. in a kind of molecular sieve catalytic oxidation removal oil product sulfide method, including making oil product, mistake
The step of hydrogen oxide is contacted with molecular sieve；The molecular sieve be M-Ti-HMS, wherein, M be except
The element selected from IB, IIB, IVB, VB, VI B, VII B or VIII race beyond Ti；The molecule
In sieve, the mol ratio of Si and M is 1～100.
2. according to claim 1 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that the mol ratio of Si and M is 10～70.
3. according to claim 2 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that the mol ratio of Si and M is 10～60.
4. according to claim 1 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that the concentration of sulfide is 0.01～20000 mg/kg in oil product.
5. according to claim 4 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that the concentration of sulfide is 0.1～8000 mg/kg in oil product.
6. according to claim 1 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that M selected from Cu, Ag, Au, Zn, Ti, Zr, V, Nb, Cr, Mo, W,
At least one in Mn, Re, Fe, Co, Ni, Ru, Rh, Pd or Pt.
7. according to claim 6 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that at least one of the M in Cu, Ag, Zn or Ni.
8. according to claim 1 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that the sulfide is thiophene, 2- methylthiophenes, 3 methyl thiophene, 2,5- dimethyl thiophenes
Fen, 2,4- thioxenes, 2,3- thioxenes, 3,4- thioxenes, tetramethyl thiophene, first
In mercaptan, ethyl mercaptan, propanethiol, isobutyl mercaptan, diethyl thioether, cos or carbon disulfide
At least one.
9. according to claim 1 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that in the molecular sieve M-Ti-HMS, Si/Ti mol ratios are 10～60.
10. according to claim 1 in molecular sieve catalytic oxidation removal oil product sulfide method,
It is characterized in that oil product is 10～100 DEG C with molecular sieve Contact Temperature, time of contact is 0.1～10 little
When, hydrogen peroxide is 3～6 with the mol ratio of sulphur in oil product, and molecular sieve consumption is oil product weight
1～3%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694601A (en) * | 2017-10-31 | 2018-02-16 | 李俊霞 | A kind of high selectivity and conversion ratio catalyst and preparation method thereof |
| CN109967129A (en) * | 2017-12-28 | 2019-07-05 | 柏美迪康环境科技（上海）股份有限公司 | A kind of composite catalyst and its preparation method and application removing stench and resourcebility recycling sulfur-containing compound |
| CN111378468A (en) * | 2020-03-20 | 2020-07-07 | 华南理工大学 | Regeneration method of waste transformer oil and regenerated transformer oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912060A (en) * | 2006-07-07 | 2007-02-14 | 中国石油化工股份有限公司 | Highly sulfur removal method of diesel oil |
| CN101255352A (en) * | 2008-04-21 | 2008-09-03 | 大连理工大学 | Method for removing sulfides in gasoline by oxidation-absorption under mild conditions |
| CN102757811A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Diesel oil oxidative desulphurization method |
-
2015
- 2015-10-12 CN CN201510655569.6A patent/CN106566577B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1912060A (en) * | 2006-07-07 | 2007-02-14 | 中国石油化工股份有限公司 | Highly sulfur removal method of diesel oil |
| CN101255352A (en) * | 2008-04-21 | 2008-09-03 | 大连理工大学 | Method for removing sulfides in gasoline by oxidation-absorption under mild conditions |
| CN102757811A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Diesel oil oxidative desulphurization method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107694601A (en) * | 2017-10-31 | 2018-02-16 | 李俊霞 | A kind of high selectivity and conversion ratio catalyst and preparation method thereof |
| CN107694601B (en) * | 2017-10-31 | 2020-05-19 | 湖北荟煌科技股份有限公司 | High-selectivity and high-conversion-rate catalyst and preparation method thereof |
| CN109967129A (en) * | 2017-12-28 | 2019-07-05 | 柏美迪康环境科技（上海）股份有限公司 | A kind of composite catalyst and its preparation method and application removing stench and resourcebility recycling sulfur-containing compound |
| CN111378468A (en) * | 2020-03-20 | 2020-07-07 | 华南理工大学 | Regeneration method of waste transformer oil and regenerated transformer oil |
| CN111378468B (en) * | 2020-03-20 | 2021-09-21 | 华南理工大学 | Regeneration method of waste transformer oil and regenerated transformer oil |
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