CN107033951B - A kind of method of nitride in removing fuel oil - Google Patents
A kind of method of nitride in removing fuel oil Download PDFInfo
- Publication number
- CN107033951B CN107033951B CN201710494037.8A CN201710494037A CN107033951B CN 107033951 B CN107033951 B CN 107033951B CN 201710494037 A CN201710494037 A CN 201710494037A CN 107033951 B CN107033951 B CN 107033951B
- Authority
- CN
- China
- Prior art keywords
- oil
- ionic liquid
- reaction kettle
- simulation
- added
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000295 fuel oil Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 23
- 150000004767 nitrides Chemical class 0.000 title claims abstract description 20
- 239000003921 oil Substances 0.000 claims abstract description 139
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 124
- 239000002608 ionic liquid Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 62
- 238000004088 simulation Methods 0.000 claims abstract description 52
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 11
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 39
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 36
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003079 shale oil Substances 0.000 claims description 25
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000002283 diesel fuel Substances 0.000 claims description 20
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 19
- 238000005259 measurement Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 13
- 229940094933 n-dodecane Drugs 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 11
- 239000011592 zinc chloride Substances 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 230000009969 flowable effect Effects 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000003475 lamination Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000005864 Sulphur Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 229910017464 nitrogen compound Inorganic materials 0.000 description 4
- 150000002830 nitrogen compounds Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002045 lasting effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- -1 nitrogenous Compound Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/06—Metal salts, or metal salts deposited on a carrier
- C10G29/12—Halides
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/26—Halogenated hydrocarbons
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of methods of nitride in removing fuel oil, it comprises the following steps that: preparing fuel oil, measure initial N contents, prepare simulation oil, prepare denitrifier, simulation oil denitrogenation, feedstock oil denitrogenation and recycling ionic liquid, first by synthesizing simulation oil identical with nitrogen content in feedstock oil, denitrogenation processing is carried out to simulation oil respectively using different kinds of ions liquid, to select two kinds of best ionic liquids of denitrification effect, for subsequent feedstock oil denitrogenation, according to the feedstock oil of different nitrogen contents, different ionic liquids can targetedly be selected, combine with iron chloride and denitrogenation is carried out to oil product, denitrification effect can be improved.The method denitrification effect of nitride is ideal in removing fuel oil of the invention, reaction condition is mild, equipment is simple, and no pollution to the environment, prospects for commercial application are very wide.
Description
Technical field
The invention belongs to oil denitrification technical fields, and in particular to a method of nitride in removing fuel oil.
Background technique
Shale oil is a kind of unconventional energy resource, stock number very abundant and reserve distribution concentration, has to be used as and takes over the energy
Great potential and advantage, be presently believed to be former oil and gas and preferably supplement the energy.The midbarrel of shale oil
Be after processed produce the good raw material of diesel oil, but impurity therein especially nitride can following process to diesel oil distillate and
Storage is brought a negative impact, and can cause environmental pollution, so in order to improve the quality of diesel oil, it is necessary to be removed therein nitrogenous
Compound.Shale oil denitrogenation method mainly has hydrodenitrogeneration technology and Non-hydrogenation technology technology, traditional hydrodenitrogeneration method at present
Harsher reaction condition is needed, and nitride can reduce the activity of catalyst, influences its denitrification effect.
Summary of the invention
To solve the deficiencies in the prior art, ideal, reaction condition temperature that the purpose of the present invention is to provide a kind of denitrification effects
With equipment is simple, in removing fuel oil of no pollution to the environment nitride method.
In order to achieve the above objectives, the present invention adopts the following technical scheme that:
A kind of method of nitride in removing fuel oil, comprises the following steps that:
S1, prepare fuel oil: appropriate shale oil being taken to be put in reaction kettle, being adjusted to temperature of reaction kettle is 50 ~ 60 DEG C, to shale
Oil carries out preheating until shale oil is added appropriate zeolite, carries out vacuum distillation processing, resulting diesel oil distillate conduct in flowable state
The feedstock oil of denitrogenation；
S2, measurement initial N contents: it takes appropriate feedstock oil to mix with solvent by quality 1:19, measures in feedstock oil respectively
Total nitrogen and basic nitrogen；
S3, preparation simulation oil: by pyridinium dissolution in dimethylbenzene, n-dodecane and hexadecane, being made simulation oil,
In, pyridine, dimethylbenzene, n-dodecane and hexadecane quality proportioning according to basic nitrogen in simulation oil it is identical as feedstock oil come
It calculates；
S4, prepare denitrifier: preparing ionic liquid [C2mim]Br、[C4mim]Br、[C2mim]Cl、[C4mim]Cl、
[C2mim]HSO4、[C4mim]HSO4、[C2mim]Cl/ZnCl2[Hnmp] H2PO4, spare；
S5, simulation oil denitrogenation: appropriate above-mentioned various ionic liquids are taken, denitrogenation processing is carried out to simulation oil respectively；It will simulation
A small amount of deionized water is added by being put in beaker after weighing in oily and above-mentioned ionic liquid, places the beaker temperature constant magnetic stirring
On device, adjusting blender temperature is 30 ~ 70 DEG C, after persistently stirring 10 ~ 30min, is taken out, 1 ~ 2h of standing, after liquid layered, is taken
Layer simulation oil measures basic nitrogen therein；The denitrification percent for calculating above-mentioned various ionic liquids selects highest two kinds of denitrification percent
Ionic liquid, respectively ionic liquid I and ionic liquid II；
S6, feedstock oil denitrogenation: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 30 ~ 40 DEG C, is slowly added to chlorine
Change iron, persistently stirs 5 ~ 10min；Adjusting temperature of reaction kettle is 40 ~ 60 DEG C, is slowly added to ionic liquid I, under constant stirring,
A small amount of deionized water and bromoethane is added, persistently stirs 10 ~ 20min；Adjust temperature of reaction kettle be 60 ~ 80 DEG C, be slowly added to from
A small amount of deionized water, 10 ~ 20min is added under constant stirring in sub- liquid；After reaction, it takes out and stands 2 ~ 3h, mixing
There is obvious lamination in liquid, takes upper layer diesel oil measurement basic nitrogen and total nitrogen content, calculates denitrification percent, and isolate lower leafing
Sub- liquid level；
S7, recycling ionic liquid: ionic liquid layer is placed in tiered container, is added and the isometric extraction of ionic liquid
Taking agent washing ionic liquid three times, layering obtains mixed ionic liquid, and mixed ionic liquid is put in drying box, dry 8 ~
10h obtains recycling ionic liquid.
Preferably, in abovementioned steps S1, reaction kettle inner tip side wall is equipped with support plate, and support plate has 2 ~ 3, and edge
The circumferencial direction of reaction kettle side wall is uniformly arranged, and baffle has been bolted on the outside of support plate, is parched if baffle is equipped with
Stomata, the diameter of air hole are 3 ~ 5mm.
More preferably, in abovementioned steps S2, using the total nitrogen content in TN-5000 sulphur/apparatus for nitrogen examination measurement feedstock oil, and
By People's Republic of China's SH/T0162-92 standard test basic nitrogen therein.
It is highly preferred that solvent is dimethylbenzene or isooctane in abovementioned steps S2.
It is further preferred that in above mentioned step S3, it is specific to prepare simulation oil step are as follows: pyridine is divided into 3 parts by quality, by two
Toluene is put in beaker, and is placed the beaker in constant temperature blender with magnetic force, and adjusting blender temperature is 45 ~ 50 DEG C, is slowly added to
First part of pyridine, and after being stirred continuously 15 ~ 25min；Adjusting blender temperature is 55 ~ 60 DEG C, and n-dodecane and positive 16 is added
Alkane, and it is slowly added to second part of pyridine, it is stirred continuously 20 ~ 30min；Adjusting blender temperature is 75 ~ 80 DEG C, is slow added into the
Three parts of pyridines persistently stir 25 ~ 35min, and reaction terminates to stand, cooling, obtain simulation oil.
Specifically, in abovementioned steps S5, the mass ratio of simulation oil, ionic liquid and deionized water is (30 ~ 50): (2 ~ 3):
(4 ~ 6).
Preferably, in abovementioned steps S6, feedstock oil, iron chloride, ionic liquid I, ionic liquid II, bromoethane and deionization
The mass ratio of water is (80 ~ 90): (0.2 ~ 0.6): (0.7 ~ 0.9): (0.7 ~ 0.9): (0.3 ~ 0.5): (0.6 ~ 0.8).
More preferably, it is additionally provided with feedstock oil pre-treatment step before abovementioned steps S6, feedstock oil is placed in reaction kettle, adjusted
Saving temperature of reaction kettle is 50 ~ 70 DEG C, and denitrifier is added, and wherein the mass ratio of feedstock oil and denitrifier is (65 ~ 75): (2 ~ 3) are held
15 ~ 25min of continuous stirring isolates upper layer feedstock oil, for use after placing 2 ~ 3h；The denitrifier is mixed for what is recycled in step S7
Close ionic liquid.
It is highly preferred that extractant is one of distilled water, petroleum ether, ether or carbon tetrachloride in abovementioned steps S7.
The invention has the beneficial effects that:
(1) the method denitrification effect of nitride is ideal in removing fuel oil of the invention, reaction condition is mild, equipment is simple
It is single, and no pollution to the environment, prospects for commercial application are very wide；
(2) first by synthesizing simulation oil identical with nitrogen content in feedstock oil, using different kinds of ions liquid respectively to mould
Quasi- oil carries out denitrogenation processing, to select two kinds of best ionic liquids of denitrification effect, subsequent feedstock oil denitrogenation is used for, according to difference
The feedstock oil of nitrogen content can select different ionic liquids, targetedly to improve denitrification effect；
(3) solvent is done using dimethylbenzene, n-dodecane and hexadecane mixing, pyridine can be made preferably to dissolve；Pyridine
By being repeatedly added portionwise into solvent, pyridine can be made sufficiently to dissolve, the nitrogen content and original in simulation oil to guarantee synthesis
Material oil is consistent；
(4) iron chloride and two kinds of ionic liquid combined denitrifications are selected, and promotor deionized water and bromoethane is added, can be mentioned
High denitrification percent can not only effectively remove basic nitrogen compound therein, can also remove certain non basic nitrogen compound and sulfide,
The quality of oil product is improved well；
(5) mixed ionic liquid after the recovery can be used for the pretreatment of feedstock oil, carry out preliminary denitrogenation processing to feedstock oil,
Removing part of nitride reduces production cost to reduce the dosage of two kinds of ionic liquids in subsequent denitrification reaction；
(6) setting of reaction kettle Internal baffle can block top duct there is a phenomenon where bumping to avoid oil product.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of reaction kettle in the embodiment of the present invention 1.
The meaning of appended drawing reference in figure: 1, reaction kettle, 2, support plate, 3, baffle.
Specific embodiment
Specific introduce is made to the present invention below in conjunction with the drawings and specific embodiments.
Embodiment 1
A kind of method of nitride in removing fuel oil, comprises the following steps that:
S1, prepare fuel oil: appropriate shale oil being taken to be put in reaction kettle, being adjusted to temperature of reaction kettle is 50 DEG C, to shale oil
Preheating is carried out until shale oil is in flowable state, appropriate zeolite is added, carries out vacuum distillation processing, resulting diesel oil distillate is as de-
The feedstock oil of nitrogen；
Referring to Fig. 1,1 inner tip side wall of reaction kettle is equipped with support plate 2, and support plate 2 has 2 ~ 3, and along 1 side of reaction kettle
The circumferencial direction of wall is uniformly arranged, and the outside of support plate 2 has been bolted baffle 3, and baffle 3 is equipped with several air holes,
The diameter of air hole is 3 ~ 5mm；
S2, measurement initial N contents: appropriate feedstock oil is taken to mix with dimethylbenzene by quality 1:19, using TN-5000 sulphur/nitrogen
Analyzer measures the total nitrogen content in feedstock oil, and presses People's Republic of China (PRC) SH/T0162-92 standard test alkali nitrogen therein
Content；
S3, preparation simulation oil: taking appropriate pyridine, and it be divided into 3 parts by quality, dimethylbenzene is put in beaker, and will
Beaker is placed in constant temperature blender with magnetic force, and adjusting blender temperature is 45 DEG C, is slowly added to first part of pyridine, and be stirred continuously
After 15min；Adjusting blender temperature is 55 DEG C, n-dodecane and hexadecane is added, and be slowly added to second part of pyridine, constantly
Stir 20min；Adjusting blender temperature is 75 DEG C, is slow added into third part pyridine, persistently stirs 25min, and reaction terminates quiet
It sets, it is cooling, obtain simulation oil；Wherein, the quality proportioning of pyridine, dimethylbenzene, n-dodecane and hexadecane is according in simulation oil
Basic nitrogen is as feedstock oil identical to be calculated；
S4, prepare denitrifier: preparing ionic liquid [C2mim]Br、[C4mim]Br、[C2mim]Cl、[C4mim]Cl、
[C2mim]HSO4、[C4mim]HSO4、[C2mim]Cl/ZnCl2[Hnmp] H2PO4, spare；
S5, simulation oil denitrogenation: appropriate above-mentioned various ionic liquids are taken, denitrogenation processing is carried out to simulation oil respectively；It will simulation
A small amount of deionized water is added by being put in beaker after weighing in oily and above-mentioned ionic liquid, simulation oil, ionic liquid and deionization
The mass ratio of water is 30:2:4；It places the beaker in constant temperature blender with magnetic force, adjusting blender temperature is 30 DEG C, lasting to stir
It after 10min, takes out, standing 1h, after liquid layered, upper layer simulation oil is taken to measure basic nitrogen therein；Calculate it is above-mentioned it is various from
The denitrification percent of sub- liquid selects the highest two kinds of ionic liquids of denitrification percent, respectively [C4Mim] Cl and [C2mim]HSO4；
S6 ', feedstock oil pretreatment: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 50 DEG C, and denitrogenation is added
Agent, wherein the mass ratio of feedstock oil and denitrifier is 65:2, persistently stirs 15min, after placing 2h, isolates upper layer feedstock oil,
For use；Denitrifier is the mixed ionic liquid recycled in step S7；
S6, feedstock oil denitrogenation: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 30 DEG C, is slowly added to chlorination
Iron persistently stirs 5min；Adjusting temperature of reaction kettle is 40 DEG C, is slowly added to [C4Mim] Cl, under constant stirring, addition is a small amount of
Deionized water and bromoethane, persistently stir 10min；Adjusting temperature of reaction kettle is 60 DEG C, is slowly added to [C2mim]HSO4, continuous
Under stirring, a small amount of deionized water, 10min is added；After reaction, it takes out and stands 2h, mixed liquor obvious lamination occurs, takes
Upper layer diesel oil measures basic nitrogen and total nitrogen content, calculates denitrification percent, and isolate lower layer's ionic liquid layer；Feedstock oil, chlorination
Iron, [C4mim]Cl、[C2mim]HSO4, bromoethane and deionized water mass ratio be 80:0.2:0.7:0.7:0.3:0.6；
S7, recycling ionic liquid: ionic liquid layer is placed in tiered container, is added and the isometric stone of ionic liquid
Three times, layering obtains mixed ionic liquid to oily ether washing ionic liquid, and mixed ionic liquid is put in drying box, dry 8h,
Obtain recycling ionic liquid.
Embodiment 2
The present embodiment is identical as the method and step of embodiment 1, and specific difference is concrete technology condition and reagent difference, packet
Include following processing step:
S1, prepare fuel oil: appropriate shale oil being taken to be put in reaction kettle, being adjusted to temperature of reaction kettle is 60 DEG C, to shale oil
Preheating is carried out until shale oil is in flowable state, appropriate zeolite is added, carries out vacuum distillation processing, resulting diesel oil distillate is as de-
The feedstock oil of nitrogen；
S2, measurement initial N contents: it takes appropriate feedstock oil to mix with isooctane by quality 1:19, measures in feedstock oil respectively
Total nitrogen and basic nitrogen；
S3, preparation simulation oil: taking appropriate pyridine, and it be divided into 3 parts by quality, dimethylbenzene is put in beaker, and will
Beaker is placed in constant temperature blender with magnetic force, and adjusting blender temperature is 50 DEG C, is slowly added to first part of pyridine, and be stirred continuously
After 25min；Adjusting blender temperature is 60 DEG C, n-dodecane and hexadecane is added, and be slowly added to second part of pyridine, constantly
Stir 30min；Adjusting blender temperature is 80 DEG C, is slow added into third part pyridine, persistently stirs 35min, and reaction terminates quiet
It sets, it is cooling, obtain simulation oil；Wherein, the quality proportioning of pyridine, dimethylbenzene, n-dodecane and hexadecane is according in simulation oil
Basic nitrogen is as feedstock oil identical to be calculated；
S4, prepare denitrifier: preparing ionic liquid [C2mim]Br、[C4mim]Br、[C2mim]Cl、[C4mim]Cl、
[C2mim]HSO4、[C4mim]HSO4、[C2mim]Cl/ZnCl2[Hnmp] H2PO4, spare；
S5, simulation oil denitrogenation: appropriate above-mentioned various ionic liquids are taken, denitrogenation processing is carried out to simulation oil respectively；It will simulation
A small amount of deionized water is added by being put in beaker after weighing in oily and above-mentioned ionic liquid, simulation oil, ionic liquid and deionization
The mass ratio of water is 50:3:6；It places the beaker in constant temperature blender with magnetic force, adjusting blender temperature is 70 DEG C, lasting to stir
It after 30min, takes out, 1 ~ 2h of standing, after liquid layered, upper layer simulation oil is taken to measure basic nitrogen therein；It calculates above-mentioned various
The denitrification percent of ionic liquid selects the highest two kinds of ionic liquids of denitrification percent, respectively [C4mim]HSO4[Hnmp] H2PO4；
S6 ', feedstock oil pretreatment: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 70 DEG C, and denitrogenation is added
Agent, wherein the mass ratio of feedstock oil and denitrifier is 75:3, persistently stirs 25min, after placing 3h, isolates upper layer feedstock oil,
For use；Denitrifier is the mixed ionic liquid recycled in step S7；
S6, feedstock oil denitrogenation: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 40 DEG C, is slowly added to chlorination
Iron persistently stirs 10min；Adjusting temperature of reaction kettle is 60 DEG C, is slowly added to [C4mim]HSO4, under constant stirring, it is added few
Deionized water and bromoethane are measured, 20min is persistently stirred；Adjusting temperature of reaction kettle is 80 DEG C, is slowly added to [Hnmp] H2PO4, not
Under disconnected stirring, a small amount of deionized water, 20min is added；After reaction, it taking out and stands 3h, there is obvious lamination in mixed liquor,
Upper layer diesel oil measurement basic nitrogen and total nitrogen content are taken, calculates denitrification percent, and isolate lower layer's ionic liquid layer；Wherein, raw material
Oil, iron chloride, [C4mim]HSO4、[Hnmp]H2PO4, bromoethane and deionized water mass ratio be 90:0.6:0.9:0.9:
0.5:0.8；
S7, recycling ionic liquid: ionic liquid layer is placed in tiered container, is added and the isometric second of ionic liquid
Ether washs ionic liquid three times, and layering obtains mixed ionic liquid, and mixed ionic liquid is put in drying box, and dry 10h is obtained
To recycling ionic liquid.
Embodiment 3
The present embodiment is identical as the method and step of embodiment 1, and specific difference is concrete technology condition and reagent difference, packet
Include following processing step:
S1, prepare fuel oil: appropriate shale oil being taken to be put in reaction kettle, being adjusted to temperature of reaction kettle is 55 DEG C, to shale oil
Preheating is carried out until shale oil is in flowable state, appropriate zeolite is added, carries out vacuum distillation processing, resulting diesel oil distillate is as de-
The feedstock oil of nitrogen；
S2, measurement initial N contents: it takes appropriate feedstock oil to mix with dimethylbenzene by quality 1:19, measures in feedstock oil respectively
Total nitrogen and basic nitrogen；
S3, preparation simulation oil: taking appropriate pyridine, and it be divided into 3 parts by quality, dimethylbenzene is put in beaker, and will
Beaker is placed in constant temperature blender with magnetic force, and adjusting blender temperature is 48 DEG C, is slowly added to first part of pyridine, and be stirred continuously
After 20min；Adjusting blender temperature is 58 DEG C, n-dodecane and hexadecane is added, and be slowly added to second part of pyridine, constantly
Stir 25min；Adjusting blender temperature is 77 DEG C, is slow added into third part pyridine, persistently stirs 30min, and reaction terminates quiet
It sets, it is cooling, obtain simulation oil；Wherein, the quality proportioning of pyridine, dimethylbenzene, n-dodecane and hexadecane is according in simulation oil
Basic nitrogen is as feedstock oil identical to be calculated；
S4, prepare denitrifier: preparing ionic liquid [C2mim]Br、[C4mim]Br、[C2mim]Cl、[C4mim]Cl、
[C2mim]HSO4、[C4mim]HSO4、[C2mim]Cl/ZnCl2[Hnmp] H2PO4, spare；
S5, simulation oil denitrogenation: appropriate above-mentioned various ionic liquids are taken, denitrogenation processing is carried out to simulation oil respectively；It will simulation
A small amount of deionized water is added by being put in beaker after weighing in oily and above-mentioned ionic liquid, simulation oil, ionic liquid and deionization
The mass ratio of water is 40:2.5:5, is placed the beaker in constant temperature blender with magnetic force, and adjusting blender temperature is 50 DEG C, lasting to stir
It after 20min, takes out, standing 1.5h, after liquid layered, upper layer simulation oil is taken to measure basic nitrogen therein；It calculates above-mentioned various
The denitrification percent of ionic liquid selects the highest two kinds of ionic liquids of denitrification percent, respectively [C2mim]HSO4[C2mim]Cl/
ZnCl2；
S6 ', feedstock oil pretreatment: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 60 DEG C, and denitrogenation is added
Agent, wherein the mass ratio of feedstock oil and denitrifier is 70:2.5, persistently stirs 20min, after placing 2.5h, isolates upper layer raw material
Oil, for use；Denitrifier is the mixed ionic liquid recycled in step S7；
S6, feedstock oil denitrogenation: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 35 DEG C, is slowly added to chlorination
Iron persistently stirs 8min；Adjusting temperature of reaction kettle is 50 DEG C, is slowly added to [C2mim]HSO4, under constant stirring, it is added a small amount of
Deionized water and bromoethane, persistently stir 15min；Adjusting temperature of reaction kettle is 70 DEG C, is slowly added to [C2mim]Cl/ZnCl2,
It is stirred continuously down, a small amount of deionized water, 15min is added；After reaction, it takes out and stands 2.5h, obvious layering occurs in mixed liquor
Phenomenon takes upper layer diesel oil measurement basic nitrogen and total nitrogen content, calculates denitrification percent, and isolate lower layer's ionic liquid layer；Raw material
Oil, iron chloride, [C2mim]HSO4、[C2mim]Cl/ZnCl2, bromoethane and deionized water mass ratio be 85:0.4:0.8:
0.8:0.4:0.7；
S7, recycling ionic liquid: ionic liquid layer is placed in tiered container, and four isometric with ionic liquid are added
Chlorination carbon washs ionic liquid three times, and layering obtains mixed ionic liquid, and mixed ionic liquid is put in drying box, dry
9h obtains recycling ionic liquid.
Comparative example 1
This comparative example is roughly the same with the nitrogen removal step in embodiment 1, and difference is no simulation oil denitrogenation and denitrifier
Difference comprises the following steps that:
S1, prepare fuel oil: appropriate shale oil being taken to be put in reaction kettle, being adjusted to temperature of reaction kettle is 50 DEG C, to shale oil
Preheating is carried out until shale oil is in flowable state, appropriate zeolite is added, carries out vacuum distillation processing, resulting diesel oil distillate is as de-
The feedstock oil of nitrogen；
S2, measurement initial N contents: appropriate feedstock oil is taken to mix with dimethylbenzene by quality 1:19, using TN-5000 sulphur/nitrogen
Analyzer measures the total nitrogen content in feedstock oil, and presses People's Republic of China (PRC) SH/T0162-92 standard test alkali nitrogen therein
Content；
S3, feedstock oil denitrogenation: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 50 DEG C, is slowly added to chlorination
Iron, feedstock oil, iron chloride mass ratio be 80:5, persistently stir 2min；After reaction, it takes out and stands 2h, mixed liquor occurs
Obvious lamination takes upper layer diesel oil measurement basic nitrogen and total nitrogen content, calculates denitrification percent；
Comparative example 2
This comparative example is roughly the same with the nitrogen removal step in embodiment 1, and difference is no simulation oil denitrogenation and denitrifier
Difference comprises the following steps that:
S1, prepare fuel oil: appropriate shale oil being taken to be put in reaction kettle, being adjusted to temperature of reaction kettle is 50 DEG C, to shale oil
Preheating is carried out until shale oil is in flowable state, appropriate zeolite is added, carries out vacuum distillation processing, resulting diesel oil distillate is as de-
The feedstock oil of nitrogen；
S2, measurement initial N contents: appropriate feedstock oil is taken to mix with dimethylbenzene by quality 1:19, using TN-5000 sulphur/nitrogen
Analyzer measures the total nitrogen content in feedstock oil, and presses People's Republic of China (PRC) SH/T0162-92 standard test alkali nitrogen therein
Content；
S3, feedstock oil denitrogenation: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 50 DEG C, is slowly added to
[C2mim]HSO4, feedstock oil and [C2mim]HSO4Mass ratio be 80:6, persistently stir 15min, after reaction, take out it is quiet
2.5h is set, there is obvious lamination in mixed liquor, takes upper layer diesel oil measurement basic nitrogen and total nitrogen content, denitrification percent is calculated, and
Isolate lower layer's ionic liquid layer.
By detection, in the diesel oil after embodiment 1, embodiment 2,2 denitrogenation processing of embodiment 3, comparative example 1 and comparative example
It is as follows: with the property analysis in feedstock oil
As can be seen from the above table, the total nitrogen content and alkali in the diesel oil after 3 denitrogenation of embodiment 1, embodiment 2 and embodiment
Nitrogen content is lower than comparative example and comparative example 2, illustrates that the denitrifier in embodiment 1, embodiment 2 and embodiment 3 can be effective
Removing shale oil diesel oil distillate in basic nitrogen compound and non basic nitrogen compound, while can also a degree of removing oil product
In sulfur-containing compound.By to after feedstock oil and denitrogenation oil product some properties measurement it is found that after denitrogenation the density of oil product and
Viscosity all decreases, this illustrates that the oil quality after denitrogenation has obtained good improvement.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
Centainly refer to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
One or more embodiment or examples in can be combined in any suitable manner.
The basic principles, main features and advantages of the invention have been shown and described above.The technical staff of the industry should
Understand, the above embodiments do not limit the invention in any form, all obtained by the way of equivalent substitution or equivalent transformation
Technical solution is fallen within the scope of protection of the present invention.
Claims (8)
1. a kind of method of nitride in removing fuel oil, which is characterized in that comprise the following steps that:
S1, prepare fuel oil: appropriate shale oil being taken to be put in reaction kettle, being adjusted to temperature of reaction kettle is 50~60 DEG C, to shale oil
Preheating is carried out until shale oil is in flowable state, appropriate zeolite is added, carries out vacuum distillation processing, resulting diesel oil distillate is as de-
The feedstock oil of nitrogen；
S2, measurement initial N contents: taking appropriate feedstock oil to mix with solvent by quality 1:19, measures the total nitrogen in feedstock oil respectively
And basic nitrogen；
S3, preparation simulation oil: by pyridinium dissolution in dimethylbenzene, n-dodecane and hexadecane, being made simulation oil, specific to prepare
Simulation oil step are as follows: pyridine is divided into 3 parts by quality, and dimethylbenzene is put in beaker, and places the beaker constant temperature blender with magnetic force
On, adjusting blender temperature is 45~50 DEG C, is slowly added to first part of pyridine, and after being stirred continuously 15~25min；Adjust stirring
Device temperature is 55~60 DEG C, n-dodecane and hexadecane is added, and be slowly added to second part of pyridine, it is stirred continuously 20~
30min；Adjusting blender temperature is 75~80 DEG C, is slow added into third part pyridine, persistently stirs 25~35min, reaction knot
Beam is stood, cooling, obtains simulation oil；Wherein, the quality proportioning of pyridine, dimethylbenzene, n-dodecane and hexadecane is according to simulation
Basic nitrogen is as feedstock oil identical in oil calculates；
S4, prepare denitrifier: preparing ionic liquid [C2mim]Br、[C4mim]Br、[C2mim]Cl、[C4mim]Cl、[C2mim]
HSO4、[C4mim]HSO4、[C2mim]Cl/ZnCl2[Hnmp] H2PO4, spare；
S5, simulation oil denitrogenation: appropriate above-mentioned various ionic liquids are taken, denitrogenation processing is carried out to simulation oil respectively；By simulation oil and
A small amount of deionized water is added by being put in beaker after weighing in above-mentioned ionic liquid, places the beaker in constant temperature blender with magnetic force,
Adjusting blender temperature is 30~70 DEG C, after persistently stirring 10~30min, is taken out, 1~2h of standing, after liquid layered, takes upper layer
Simulation oil measures basic nitrogen therein；The denitrification percent for calculating above-mentioned various ionic liquids, select highest two kinds of denitrification percent from
Sub- liquid, respectively ionic liquid I and ionic liquid II；
The pretreatment of S6 ' feedstock oil: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 50~70 DEG C, and denitrifier is added,
Wherein the mass ratio of feedstock oil and denitrifier is (65~75): (2~3), persistently stirs 15~25min, after placing 2~3h, point
Upper layer feedstock oil is separated out, for use；
S6, feedstock oil denitrogenation: feedstock oil is placed in reaction kettle, and adjusting temperature of reaction kettle is 30~40 DEG C, is slowly added to chlorination
Iron persistently stirs 5~10min；Adjusting temperature of reaction kettle is 40~60 DEG C, is slowly added to ionic liquid I, under constant stirring,
A small amount of deionized water and bromoethane is added, persistently stirs 10~20min；Adjusting temperature of reaction kettle is 60~80 DEG C, is slowly added to
A small amount of deionized water, 10~20min is added under constant stirring in ionic liquid II；After reaction, it takes out and stands 2~3h,
There is obvious lamination in mixed liquor, takes upper layer diesel oil measurement basic nitrogen and total nitrogen content, calculates denitrification percent, and isolate down
Layer ionic liquid layer；
S7, recycling ionic liquid: ionic liquid layer is placed in tiered container, is added and the isometric extractant of ionic liquid
Wash ionic liquid three times, layering obtains mixed ionic liquid, and mixed ionic liquid is put in drying box, dry 8~10h,
Obtain recycling ionic liquid.
2. the method for nitride in a kind of removing fuel oil according to claim 1, which is characterized in that the step S1
In, reaction kettle inner tip side wall is equipped with support plate, and support plate has 2~3, and uniform along the circumferencial direction of reaction kettle side wall
It is arranged, baffle has been bolted on the outside of the support plate, the baffle is equipped with several air holes, the diameter of air hole
For 3~5mm.
3. the method for nitride in a kind of removing fuel oil according to claim 1, which is characterized in that the step S2
In, using the total nitrogen content in TN-5000 sulphur/apparatus for nitrogen examination measurement feedstock oil, and press People's Republic of China (PRC) SH/T0162-92
Standard test basic nitrogen therein.
4. the method for nitride in a kind of removing fuel oil according to claim 1, which is characterized in that the step S2
In, solvent is dimethylbenzene or isooctane.
5. the method for nitride in a kind of removing fuel oil according to claim 1, which is characterized in that the step S5
In, the mass ratio of simulation oil, ionic liquid and deionized water is (30~50): (2~3): (4~6).
6. the method for nitride in a kind of removing fuel oil according to claim 1, which is characterized in that the step S6
In, feedstock oil, iron chloride, ionic liquid I, ionic liquid II, bromoethane and deionized water mass ratio be (80~90): (0.2
~0.6): (0.7~0.9): (0.7~0.9): (0.3~0.5): (0.6~0.8).
7. the method for nitride in a kind of removing fuel oil according to claim 1, which is characterized in that the step S6 '
In, denitrifier is the mixed ionic liquid recycled in step S7.
8. the method for nitride in a kind of removing fuel oil according to claim 1, which is characterized in that the step S7
In, extractant is one of distilled water, petroleum ether, ether or carbon tetrachloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710494037.8A CN107033951B (en) | 2017-06-26 | 2017-06-26 | A kind of method of nitride in removing fuel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710494037.8A CN107033951B (en) | 2017-06-26 | 2017-06-26 | A kind of method of nitride in removing fuel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107033951A CN107033951A (en) | 2017-08-11 |
| CN107033951B true CN107033951B (en) | 2019-04-19 |
Family
ID=59541426
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710494037.8A Active CN107033951B (en) | 2017-06-26 | 2017-06-26 | A kind of method of nitride in removing fuel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107033951B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110408423A (en) * | 2019-08-09 | 2019-11-05 | 磁悬浮润滑油(苏州)有限公司 | A method of Sulfur content in Fuel Oil compound is removed using modified poly (ethylene glycol) |
| CN114621788B (en) * | 2020-12-08 | 2023-07-25 | 中国石油天然气股份有限公司 | Catalytic diesel denitrification and hydrotreatment method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277867A (en) * | 2013-07-12 | 2015-01-14 | 中国石油天然气股份有限公司 | Method for removing sulfur-containing compounds in fuel oil by using Lewis acid ionic liquid |
| CN105400541A (en) * | 2015-09-30 | 2016-03-16 | 青岛农业大学 | Selective removal of basic nitrogen compounds in oil products using carboxyl-functionalized acid ionic liquid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100270211A1 (en) * | 2009-04-27 | 2010-10-28 | Saudi Arabian Oil Company | Desulfurization and denitrogenation with ionic liquids and metal ion systems |
| MX2011007922A (en) * | 2011-07-27 | 2013-02-07 | Mexicano Inst Petrol | Denitrogenation of hydrocarbons by liquid-liquid extraction using ionic liquids. |
-
2017
- 2017-06-26 CN CN201710494037.8A patent/CN107033951B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277867A (en) * | 2013-07-12 | 2015-01-14 | 中国石油天然气股份有限公司 | Method for removing sulfur-containing compounds in fuel oil by using Lewis acid ionic liquid |
| CN105400541A (en) * | 2015-09-30 | 2016-03-16 | 青岛农业大学 | Selective removal of basic nitrogen compounds in oil products using carboxyl-functionalized acid ionic liquid |
Non-Patent Citations (3)
| Title |
|---|
| "［Amim］Cl/ZnCl2离子液体脱除燃料油中碱性氮化物";刘洁等;《燃料化学学报》;20161031;第44卷(第10期);第1233-1239页 |
| "咪唑类离子液体脱除油品中非碱性氮化物";刘洁等;《化工新型材料》;20161031;第44卷(第10期);第185-187页 |
| "磷酸基咪唑离子液体脱除煤焦油柴油馏分中的氮化物";苏晓琳等;《化工进展》;20161231;第35卷(第4期);第1081-1806页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107033951A (en) | 2017-08-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107033951B (en) | A kind of method of nitride in removing fuel oil | |
| CN106496264A (en) | A kind of bisphenol-A is double（Diphenyl phosphoester）Continuous preparation method | |
| CN105439820A (en) | Method for innocently treating organic waste liquid generated in BDO production | |
| CN106749890A (en) | A kind of PAMC reversed-phase emulsion and preparation method thereof | |
| CN109374599A (en) | The rapid assay methods of 20 kinds of impurity elements in a kind of ingot casting bronze | |
| CN101580639A (en) | Lignin modified asphalt composition and preparation method thereof | |
| CN1613546A (en) | Method for separating chromiumin leather-making waste water by milked liquid and membrane separating method | |
| CN105061624B (en) | A kind of modified guar gum and preparation method thereof | |
| CN106565003A (en) | Production process of high-efficiency and high-concentration polyaluminum ferric chloride sulfate | |
| CN1050163C (en) | Method of producing polyurethane synthetic leather by using concave-convex clay rod as filler | |
| CN108193526A (en) | A kind of digital printing gum of activity and preparation method thereof | |
| CN106277045B (en) | The technique that a kind of titanium dioxide hydrochloric acid residue resource recycles | |
| CN205701243U (en) | A kind of plastic foil produces uses dyestuff circulating device | |
| CN104845662A (en) | A method for extracting phenolic compounds in coal liquefaction oil | |
| WO2009121599A1 (en) | Method for the neutralization of acids or acid mixtures from the photovoltaic industry | |
| CN101665870A (en) | Method for preventing interfacial crud during vanadium-chromium extraction and separation | |
| CN104631180A (en) | Methods for preparing and using dissociation treatment agent for waste impregnated paper with wet-strength | |
| WO2017012710A1 (en) | Method for reducing trivalent iron in the production of titanium dioxide according to the sulfate method | |
| CN106630919A (en) | Formula of light-weight counter-weight block for elevator and preparation technology thereof | |
| CN207828186U (en) | A kind of slurry oil prepares the small test device of mesophase pitch | |
| CN101381096A (en) | Method for reproducing copper sulfate using waste and old covered copper plate | |
| CN204544954U (en) | A kind of containing phenol wastes reduction treating apparatus | |
| CN106517376A (en) | Paper-making sewage treatment agent as well as preparation method and application of paper-making sewage treatment agent | |
| CN108359807A (en) | The process that the waste and old plugs of H13 recycle | |
| CN111455705A (en) | Method for making corrugated pulp from moldy tobacco leaves and other tobacco waste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |