CN107916130B - The method of mercaptan thioetherification - Google Patents
The method of mercaptan thioetherification Download PDFInfo
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- CN107916130B CN107916130B CN201610882168.9A CN201610882168A CN107916130B CN 107916130 B CN107916130 B CN 107916130B CN 201610882168 A CN201610882168 A CN 201610882168A CN 107916130 B CN107916130 B CN 107916130B
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- mercaptan
- catalyst
- nitrogenous compound
- metal
- thioetherification
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/14—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with moving solid particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The present invention relates to a kind of methods of mercaptan thioetherification under room temperature~80 DEG C, normal pressure, to make mercaptan be converted to thioether using a kind of functionalized ion liquid being made of alkyl pyridine, imidazoles or ethamine nitrogenous compound and metal or non-metallic halide as catalyst.Wherein the molar ratio of metal or non-metallic halide and imidazoles or ethamine nitrogenous compound is 1:7 to 1:1, catalyst amount is the 5-40%wt of material quantity, the technical solution of reaction time 10-60min reduces sulfur in gasoline alcohol content, can be used for mercaptan thioetherification field.
Description
Technical field
The present invention relates to a kind of methods of mercaptan thioetherification, especially the method for reducing sulfur in gasoline alcohol content.
Background technique
In recent years, global crude oil holds at high price, the rapid growth of ethylene production capacity, and aromatic hydrocarbons is in strong demand.Cracking stock is more
Memberization and heaviness, in poor quality become normality, this will lead to impurity content, particularly organic sulfur equal size in drippolene
It is exceeded, affect activity and the service life of traditional catalyst.
In the deep desulfuration field of gasoline, diesel oil, foreign countries have developed the work of new production super low-sulfur oil successively at present
Skill technology, wherein what the CD Hydro&CDHDS technique and Axens company, France developed with the CD TECH company in the U.S. were developed
Prime G+ technique has broad application prospects.The two techniques are under the operating condition of mitigation by catalytically cracked gasoline
(FCCG) alkadienes and mercaptan in occur thioetherification reaction by the effect of catalyst and form high boiling thioether, and subsequent
Fractionating device enter weight gasoline component (HCN), obtain no sulphur and be rich in alkene light petrol (LCN), it is straight both to have avoided LCN
It taps into and causes loss of octane number into hydrodesulfurizationunit unit generation olefin saturation, meanwhile, the alkadienes in this reaction process
Monoolefine is generated also by selective hydrogenation.The treatment process can simultaneously in removing gasoline mercaptan and alkadienes.By sulphur
Technique of the etherification technology in conjunction with hydrodesulfurization has the characteristics that gasoline desulfurization degree is high, alkene saturation factor is low and octane number is high, sulphur
That isolates after etherification process carries out hydrodesulfurization processing rich in sulphur, HCN without alkadienes, can be improved catalyst stability and
Service life extends the operation cycle of device.
Foreign countries are concentrated mainly on process aspect to the research of the technology at present, not yet to catalyst used in thioetherification reaction
See special report, the catalyst used mainly uses Ni the and Pd hydrogenation catalyst of the marketization, to diene hydrogenation and sulphur
Etherification reaction all has higher catalytic activity.
Chinese patent CN102125846B discloses a kind of mercaptan etherification catalyst, using through 0.1wt%~20wt% gold
Belong to the alumina support of oxide modifying, loads the oxide of 5wt%~40wt%Fe and/or Ni, in addition and/or 1wt%~
The oxide of the Mo of 10wt%, for removing mercaptan and alkadienes in catalytic gasoline of whole fraction.
Chinese patent CN104971724A discloses a kind of preparation method of low temperature mercaptan thioetherification catalyst, uses with nothing
The Al of machine acid or modified with organic acids2O3Carrier is loaded, and the bimetallic Sulfur-Vapor of Lower Temperature containing nickel oxide and iron oxide 8-40% is obtained
Catalyst for etherification has good removal effect to impurity such as hydrogen sulfide micro in liquefied petroleum gas, carbonyl sulfurs.
Chinese patent CN105126883A discloses the low temperature thioetherification bimetallic catalyst of a kind of phosphorus or boron modification, this is urged
Agent is using the aluminium oxide of phosphorus or boron modification as carrier, and using nickel, iron as active component, the catalyst invented is under low reaction temperatures
(90 DEG C of <) shows excellent thioetherification activity, and with good stability.
Above-mentioned patent primarily directed to low content, small molecule mercaptan removing, for higher amount under low temperature and higher
The removing of molecule mercaptan is not directed to.
Summary of the invention
The object of the present invention is to provide a kind of methods of mercaptan thioetherification, especially for reducing sulfur in gasoline alcohol content
Method.
In order to solve the above technical problems, The technical solution adopted by the invention is as follows: being selected from alkyl using by nitrogenous compound
The functionalized ion liquid that at least one of pyridine, imidazoles or ethamine nitrogenous compound and metal or non-metallic halide are constituted
As catalyst, under room temperature~80 DEG C, normal pressure, mercaptan is made to be converted to thioether.Wherein metal or non-metallic halide and imidazoles
Or the molar ratio of ethamine nitrogenous compound be 7:1 to 1:1, catalyst amount be material quantity 5~40%wt, the reaction time 10~
60min。
In above-mentioned technical proposal, nitrogenous compound 1- butyl-pyridinium, 1- butyl -3- methylimidazole or hydrochloric acid are preferably used
Diethylamine, metal or non-metallic halide are in alchlor, ferric trichloride, zinc dichloride, boron trifluoride, phosphorus pentafluoride
The molar ratio of at least one, metal or non-metallic halide and nitrogenous compound is 6:1 to 1:1, and catalyst amount is material quantity
10-30%wt, reaction temperature be room temperature~60 DEG C, the reaction time be 20~60min.
Catalyst of the present invention the preparation method comprises the following steps: suitable solid metal halogenide is taken, such as aluminum trichloride (anhydrous) and solid-state
Alkyl pyridine, alkyl imidazole or triethylamine hydrochloride, mixed under room temperature with solvent, such as hexamethylene, temperature programming dissolution, i.e. shape
At a kind of at room temperature or close to the clear liquid being in a liquid state at room temperature, i.e. ionic liquid.Wherein, metal or non-metallic halide
It is 7:1 to 1:1 with the molar ratio of imidazoles or ethamine nitrogenous compound.
Implementation process of the invention is: 5 grams of above-mentioned catalyst is added in the three-necked flask equipped with stirring, reflux unit,
25-200 grams of hydrocarbon material containing mercaptan is added, under stirring, room temperature or is heated to certain temperature, keeps reaction 10-60 minutes.So
After be cooled to room temperature, collect upper layer hydrocarbon material, analyzed.The ionic-liquid catalyst of lower layer, can be recycled.
Below by embodiment, the present invention is further elaborated.But these embodiments are not anyway to the present invention
Range be construed as limiting.
Specific embodiment
[embodiment 1]
5 grams of ionic liquids being made of aluminum trichloride (anhydrous) and diethylamine hydrochloride are taken, wherein aluminum trichloride (anhydrous) and hydrochloric acid
The molar ratio of diethylamine is 2:1, is put into equipped with stirring, in the three-necked flask of reflux unit, the hydrocarbon material containing mercaptan is added
It 12.5 grams, reacts 60 minutes for (20 DEG C) at room temperature, sampling analysis, the results are shown in Table 1 after reaction.
[embodiment 2]
5 grams of ionic liquids being made of aluminum trichloride (anhydrous) and 1- butyl-pyridinium are taken, wherein aluminum trichloride (anhydrous) and hydrochloric acid
The molar ratio of diethylamine is 2:1, is put into equipped with stirring, in the three-necked flask of reflux unit, the hydrocarbon material 100 containing mercaptan is added
Gram, 40 DEG C are reacted 30 minutes, and sampling analysis, the results are shown in Table 1 after reaction.
[embodiment 3]
5 grams of ionic liquids being made of zinc dichloride and diethylamine hydrochloride are taken, wherein zinc dichloride and diethylamine hydrochloride
Molar ratio is 6:1, is put into equipped with stirring, in the three-necked flask of reflux unit, 15 grams of hydrocarbon material containing mercaptan are added, 60 DEG C anti-
It answers 30 minutes, sampling analysis, the results are shown in Table 1 after reaction.
[embodiment 4]
5 grams of ionic liquids being made of boron trifluoride and 1- butyl -3- methylimidazole are taken, wherein boron trifluoride and 1- fourth
The molar ratio of base -3- methylimidazole is 2:1, is put into equipped with stirring, in the three-necked flask of reflux unit, the hydro carbons containing mercaptan is added
15 grams of material, 60 DEG C are reacted 40 minutes, and sampling analysis, the results are shown in Table 1 after reaction.
[embodiment 5]
5 grams of ionic liquids being made of phosphorus pentafluoride and 1- butyl -3- methylimidazole are taken, wherein phosphorus pentafluoride and 1- fourth
The molar ratio of base -3- methylimidazole is 2:1, is put into equipped with stirring, in the three-necked flask of reflux unit, the hydro carbons containing mercaptan is added
15 grams of material, 60 DEG C are reacted 60 minutes, and sampling analysis, the results are shown in Table 1 after reaction.
[embodiment 6]
5 grams of ionic liquids being made of ferric trichloride and diethylamine hydrochloride are taken, wherein ferric trichloride and diethylamine hydrochloride
Molar ratio is 5:1, is put into equipped with stirring, in the three-necked flask of reflux unit, 15 grams of hydrocarbon material containing mercaptan are added, 60 DEG C anti-
It answers 40 minutes, sampling analysis, the results are shown in Table 1 after reaction.
[embodiment 7]
5 grams of ionic liquids being made of zinc dichloride, 1- butyl -3- methylimidazole and diethylamine hydrochloride are taken, wherein 1- fourth
The molar ratio of base -3- methylimidazole and diethylamine hydrochloride is 1:1, and the molar ratio of zinc dichloride and nitrogenous compound is 6:1, is put into
Equipped with stirring, in the three-necked flask of reflux unit, 15 grams of hydrocarbon material containing mercaptan are added, 60 DEG C are reacted 30 minutes, reaction knot
Sampling analysis after beam, the results are shown in Table 1.
[embodiment 8]
5 grams of ionic liquids being made of boron trifluoride, 1- butyl-pyridinium and 1- butyl -3- methylimidazole are taken, wherein 1- fourth
The molar ratio of yl pyridines and 1- butyl -3- methylimidazole is 1:1；The molar ratio of boron trifluoride and nitrogenous compound is 2:1, is put into
Equipped with stirring, in the three-necked flask of reflux unit, 15 grams of hydrocarbon material containing mercaptan are added, 60 DEG C are reacted 40 minutes, reaction knot
Sampling analysis after beam, the results are shown in Table 1.
[embodiment 9]
Take 5 grams of ionic liquids being made of ferric trichloride, 1- butyl-pyridinium, 1- butyl -3- methylimidazole and diethylamine hydrochloride
Body, wherein the molar ratio of 1- butyl-pyridinium, 1- butyl -3- methylimidazole and diethylamine hydrochloride is 1:1:1；Ferric trichloride and nitrogenous
The molar ratio of compound is 5:1, is put into equipped with stirring, in the three-necked flask of reflux unit, the hydrocarbon material 15 containing mercaptan is added
Gram, 60 DEG C are reacted 40 minutes, and sampling analysis, the results are shown in Table 1 after reaction.
[embodiment 10]
5 grams of ionic liquids being made of aluminum trichloride (anhydrous), 1- butyl-pyridinium and diethylamine hydrochloride are taken, wherein anhydrous trichlorine
The molar ratio for changing aluminium and nitrogenous compound (1- butyl-pyridinium+diethylamine hydrochloride) is 2:1, and the ratio of two kinds of nitrogenous compounds is 1:
1, it is put into equipped with stirring, in the three-necked flask of reflux unit, 12.5 grams of hydrocarbon material containing mercaptan is added, (20 DEG C) are anti-at room temperature
It answers 60 minutes, sampling analysis, the results are shown in Table 1 after reaction.
1 reaction result of table
Seen from table 1, catalyst of the present invention can realize the conversion of mercaptan under conditions of quite mild.
Claims (7)
1. a kind of method of mercaptan thioetherification, it is characterised in that using by least one in alkyl pyridine, imidazoles or ethamine
The functionalized ion liquid that the nitrogenous compound and metal or non-metallic halide of kind are constituted is as catalyst, in room temperature~80
DEG C, under normal pressure, mercaptan is made to be converted to thioether；Wherein the molar ratio of metal or non-metallic halide and nitrogenous compound be 7:1 extremely
1:1, catalyst amount are the 5-40%wt, reaction time 10-60min of material quantity.
2. the method for mercaptan thioetherification according to claim 1, it is characterised in that the nitrogenous compound is selected from 1- butyl
At least one of pyridine, 1- butyl -3- methylimidazole or diethylamine hydrochloride.
3. the method for mercaptan thioetherification according to claim 1, it is characterised in that the metal or non-metallic halide choosing
From at least one of alchlor, ferric trichloride, zinc dichloride, boron trifluoride, phosphorus pentafluoride.
4. the method for mercaptan thioetherification according to claim 1, it is characterised in that the metal or non-metallic halide with
The molar ratio of nitrogenous compound is 6:1 to 1:1.
5. the method for mercaptan thioetherification according to claim 1, it is characterised in that the catalyst amount is material quantity
10-30%wt.
6. the method for mercaptan thioetherification according to claim 1, it is characterised in that the reaction temperature is room temperature~60 DEG C.
7. the method for mercaptan thioetherification according to claim 1, it is characterised in that the reaction time is 20-60min.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479738A (en) * | 2014-12-16 | 2015-04-01 | 西安石油大学 | Catalytically cracked gasoline deep desulfurization combined technique |
| CN104511287A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | A preparing method of a mercaptan etherification catalyst |
| CN105562019A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Mercaptan thioetherfication catalyst |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104511287A (en) * | 2013-09-29 | 2015-04-15 | 中国石油化工股份有限公司 | A preparing method of a mercaptan etherification catalyst |
| CN105562019A (en) * | 2014-10-14 | 2016-05-11 | 中国石油化工股份有限公司 | Mercaptan thioetherfication catalyst |
| CN104479738A (en) * | 2014-12-16 | 2015-04-01 | 西安石油大学 | Catalytically cracked gasoline deep desulfurization combined technique |
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