CN107159162B - Polymerization ring dextrin desulfurizer for light oil product desulfurization - Google Patents
Polymerization ring dextrin desulfurizer for light oil product desulfurization Download PDFInfo
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- CN107159162B CN107159162B CN201710425747.5A CN201710425747A CN107159162B CN 107159162 B CN107159162 B CN 107159162B CN 201710425747 A CN201710425747 A CN 201710425747A CN 107159162 B CN107159162 B CN 107159162B
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- cyclodextrin
- crosslinking agent
- desulfurizer
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- toluene
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- 238000006477 desulfuration reaction Methods 0.000 title abstract description 21
- 230000023556 desulfurization Effects 0.000 title abstract description 21
- 238000006116 polymerization reaction Methods 0.000 title description 23
- 229920001353 Dextrin Polymers 0.000 title description 2
- 239000004375 Dextrin Substances 0.000 title description 2
- 235000019425 dextrin Nutrition 0.000 title description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 99
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 42
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 28
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 28
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 28
- 229960004853 betadex Drugs 0.000 claims abstract description 28
- GDSRMADSINPKSL-HSEONFRVSA-N gamma-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO GDSRMADSINPKSL-HSEONFRVSA-N 0.000 claims abstract description 24
- 229940080345 gamma-cyclodextrin Drugs 0.000 claims abstract description 24
- 229920001450 Alpha-Cyclodextrin Polymers 0.000 claims abstract description 16
- HFHDHCJBZVLPGP-RWMJIURBSA-N alpha-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO HFHDHCJBZVLPGP-RWMJIURBSA-N 0.000 claims abstract description 16
- 229940043377 alpha-cyclodextrin Drugs 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 78
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 73
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000012046 mixed solvent Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 11
- 150000003568 thioethers Chemical class 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 description 25
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 230000003009 desulfurizing effect Effects 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 6
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical class S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 4
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 229930192474 thiophene Natural products 0.000 description 4
- 229940097362 cyclodextrins Drugs 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PUPKPAZSFZOLOR-UHFFFAOYSA-N n,n-dimethylformamide;toluene Chemical compound CN(C)C=O.CC1=CC=CC=C1 PUPKPAZSFZOLOR-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a polymerized cyclodextrin desulfurizer for light oil product desulfurization, which is formed by one or a compound of active components α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin and a crosslinking agent tetrafluoroterephthalonitrile.
Description
Technical Field
The invention relates to a polymerization cyclodextrin desulfurizing agent for desulfurizing a light oil product, belonging to the field of petroleum processing.
Background
Petroleum, as the most important energy fuel, plays an irreplaceable role in the rapid growth of global economy. With the continuous development of society, the dependence of human beings on petroleum increases day by day, and heavy petroleum resources with good development prospect become one of the important energy resources in the 21 st century. Heavy oil, also called unconventional crude oil, has a relatively large molecular weight and a complex structure, and contains a large amount of non-hydrocarbon compounds, wherein the total amount of miscellaneous elements such as S, N is generally 1% to 5%. SO generated after combustion of sulfur-containing substances in oilxCauses great pollution to the environment and does not meet the requirements of environmental protection regulations. The main forms of sulfur in light oil products include mercaptans, thioethers, disulfides, and thiophenes. Wherein the thiophene sulfides account for about60% of the sulfur content and is difficult to remove by conventional hydrodesulfurization processes. Therefore, in order to reduce the sulfur content, realize the deep desulfurization of the oil product and produce clean oil products, the thiophene sulfides in the oil product must be removed. At present, a few methods for deep desulfurization are really efficient and environmentally friendly, and a deep desulfurization technology which is low in cost, mild in operation condition and environmentally friendly needs to be developed urgently.
Supramolecular chemistry is an emerging frontier subject that has developed rapidly based on the development of macrocyclic compounds such as crown ethers, cyclodextrins, and the like, as well as the study of self-assembly. Among them, cyclodextrin is the most studied, and natural and chemically modified cyclodextrins have good hydrophobic cavities and can include various organic molecules and inorganic molecules to form supramolecular inclusion compounds.
According to researches, β -CD aqueous solution can remove thiophene sulfides in light oil in an inclusion manner, but the desulfurization rate is not high (Sunyan. β -basic research on organic sulfide inclusion by cyclodextrin [ D ]. Qingdao: China Petroleum university (east China), 2007.). based on earlier researches, different types of cyclodextrin are bonded through a cross-linking agent to synthesize the polymerized cyclodextrin desulfurizing agent, the regeneration is convenient, and different types of sulfides in the light oil can be removed efficiently.
Disclosure of Invention
The invention utilizes tetrafluoroterephthalonitrile as a crosslinking agent to polymerize one or a compound of α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin serving as desulfurization active components, synthesizes and obtains a polymerized cyclodextrin desulfurizer, realizes the efficient removal of different types of sulfides in light oil products, and ensures that the developed polymerized cyclodextrin desulfurizer is convenient to regenerate and can be recycled for multiple times, thereby meeting the requirements of green chemistry and chemical engineering.
The technical scheme of the polymerization cyclodextrin desulfurizer for light oil product desulfurization comprises the following steps:
the polymerization cyclodextrin desulfurizer consists of active components α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin or a compound of the active components and a crosslinking agent tetrafluoroterephthalonitrile, wherein the mass ratio of the active components to the crosslinking agent is 5-0.5: 1.
The synthetic method of the polymerization cyclodextrin fine desulfurizer comprises the following steps of putting active components α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin in one or a compound mode, putting a crosslinking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of the N, N-dimethylformamide to the toluene is 8:1), reacting for 24-48 hours at 90-110 ℃, filtering reaction liquid after the reaction is finished, washing a filter cake by using hydrochloric acid, water and isopropanol in sequence, and freeze-drying to constant weight to obtain the polymerization cyclodextrin fine desulfurizer.
The mass of the catalyst sodium carbonate is the sum of the mass of one or a compound of active components α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin and the mass of a cross-linking agent tetrafluoroterephthalonitrile.
The mass ratio of the total mass of the active components α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin, the cross-linking agent tetrafluoroterephthalonitrile and the catalyst sodium carbonate to the mixed solvent of N, N-dimethylformamide and toluene is 0.05-0.20: 1.
The polymerization cyclodextrin desulfurizer is used for removing different types of sulfides in light oil products, and mainly aims at thiophene sulfides (thiophene, benzothiophene and dibenzothiophene).
The method for removing the sulfide in the light oil product by using the polymerized cyclodextrin desulfurizer of the invention comprises the following steps: under normal pressure, mixing a desulfurizing agent and a light oil product containing sulfide according to a certain agent-oil mass ratio, and desulfurizing at a certain temperature and for a certain time; wherein the mass ratio of the agent to the oil is 1:60-1:10, the desulfurization temperature is 25-50 ℃, and the desulfurization time is 30-120 minutes.
The polymerization cyclodextrin desulfurizer of the invention has the advantages that:
(1) the invention discloses a polymerization cyclodextrin desulfurizing agent for removing sulfide in light oil, which mainly realizes a desulfurization process by virtue of the supermolecule inclusion effect of cyclodextrin on sulfide, and simultaneously utilizes a cross-linking agent to polymerize a plurality of cyclodextrins, wherein the polymerization cyclodextrin desulfurizing agent has a certain specific surface area and pore channels, and can efficiently remove different types of sulfide in the light oil.
(2) The polymerization cyclodextrin desulfurizer of the invention has simple preparation steps, is easy to operate and can easily realize mass production.
Drawings
FIG. 1 shows the effect of the desulfurizing agent of the present invention on the removal of dibenzothiophene (1, α -CDP; 2, β -CDP; 3, γ -CDP; 4, (β, γ) -CDP; 5, (α, γ) -CDP), FIG. 2 shows the effect of the desulfurizing agent of the present invention β -CDP on the removal of different sulfides (1, t-butylmercaptan; 2, ethylsulfide; 3, diethyldisulfide; 4, thiophene; 5, thiophenol; 6, benzothiophene; 7, dibenzothiophene), FIG. 3 shows the effect of the desulfurizing agent of the present invention β -CDP, β -CD, activated carbon on dibenzothiophene (1, β -CDP; 2, β -CD; 3, activated carbon)
Detailed Description
In order that the present disclosure may be more readily and clearly understood, reference will now be made in detail to specific embodiments of the present disclosure. The invention is not limited to the examples given.
Example 1
The polymerization cyclodextrin fine desulfurizer A comprises an active component α -cyclodextrin and a crosslinking agent tetrafluoroterephthalonitrile, wherein the mass ratio of the active component α -cyclodextrin to the crosslinking agent tetrafluoroterephthalonitrile is 0.5:1, the synthesis step is that the active component α -cyclodextrin, the crosslinking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate are placed in a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of N, N-dimethylformamide to toluene is 8:1), wherein the mass ratio of α -cyclodextrin, the crosslinking agent, the catalyst, and the mixed solvent of N, N-dimethylformamide and toluene is 0.01: 0.02:0.03:1, the reaction is carried out for 24 hours at 90 ℃, after the reaction is finished, the reaction liquid is filtered, the filter cake is sequentially washed by hydrochloric acid, water and isopropanol, and the filter cake is frozen and dried to constant weight, and the polymerization cyclodextrin desulfurizer A is obtained.
Example 2
The polymerization cyclodextrin fine desulfurizer B consists of an active component β -cyclodextrin and a crosslinking agent tetrafluoroterephthalonitrile, wherein the mass ratio of the active component β -cyclodextrin to the crosslinking agent tetrafluoroterephthalonitrile is 1: 1.5. the synthesis step comprises the steps of placing β -cyclodextrin, the crosslinking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of N, N-dimethylformamide to toluene is 8:1), reacting β -cyclodextrin, the crosslinking agent, the catalyst and the mixed solvent of N, N-dimethylformamide and toluene at the mass ratio of 0.01: 0.015:0.025:1 for 24 hours at 95 ℃, filtering a reaction liquid after the reaction is finished, sequentially washing a filter cake with hydrochloric acid, water and isopropanol, and freezing and drying to constant weight to obtain the polymerization cyclodextrin desulfurizer B.
Example 3
The polymerization cyclodextrin fine desulfurizer C comprises an active component β -cyclodextrin and a crosslinking agent tetrafluoroterephthalonitrile, wherein the mass ratio of the active component β -cyclodextrin to the crosslinking agent tetrafluoroterephthalonitrile is 5:1, and the synthesis step comprises the steps of placing the active component β -cyclodextrin, the crosslinking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of N, N-dimethylformamide to toluene is 8:1), reacting β -cyclodextrin, the crosslinking agent, the catalyst and the mixed solvent of N, N-dimethylformamide and toluene at the mass ratio of 0.05: 0.01:0.06:1 for 48 hours at 100 ℃, filtering a reaction liquid after the reaction is finished, washing a filter cake with hydrochloric acid, water and isopropanol in sequence, and freeze-drying the filter cake to constant weight to obtain the polymerization cyclodextrin desulfurizer C.
Example 4
The polymerized cyclodextrin fine desulfurizer D consists of an active component gamma-cyclodextrin and a cross-linking agent tetrafluoroterephthalonitrile, wherein the mass ratio of the active component gamma-cyclodextrin to the cross-linking agent tetrafluoroterephthalonitrile is 1:1. The synthesis steps are as follows: placing an active component gamma-cyclodextrin, a cross-linking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of the N, N-dimethylformamide to the toluene is 8:1), wherein the ratio of the gamma-cyclodextrin: a crosslinking agent: catalyst: the mass ratio of the N, N-dimethylformamide-toluene mixed solvent to the mixed solvent is 0.05: 0.05:0.10:1, reacting for 36 hours at 110 ℃; and after the reaction is finished, filtering the reaction solution, washing a filter cake by using hydrochloric acid, water and isopropanol in sequence, and freeze-drying to constant weight to obtain the polymerized cyclodextrin desulfurizer D.
Example 5
The polymeric cyclodextrin fine desulfurizer E consists of active components β -cyclodextrin, gamma-cyclodextrin and a crosslinking agent tetrafluoroterephthalonitrile, wherein the mass ratio of the active components β -cyclodextrin, the gamma-cyclodextrin and the crosslinking agent tetrafluoroterephthalonitrile is 1.5:1.5:1, and the synthetic step comprises the steps of placing the active components β -cyclodextrin, the gamma-cyclodextrin, the crosslinking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of the N, N-dimethylformamide to the toluene is 8:1), wherein the mass ratio of the β -cyclodextrin, the gamma-cyclodextrin, the crosslinking agent, the catalyst and the mixed solvent of the N, N-dimethylformamide and toluene is 0.06: 0.02:0.08:1, reacting for 40 hours at 105 ℃, filtering a reaction liquid after the reaction is finished, sequentially washing a filter cake with hydrochloric acid, water and isopropanol, and freeze-drying until the weight of the polymeric cyclodextrin E is reduced.
Example 6
The polymerization cyclodextrin fine desulfurizer F comprises active components of β -cyclodextrin, gamma-cyclodextrin and a crosslinking agent of tetrafluoroterephthalonitrile, wherein the mass ratio of the active components of β -cyclodextrin, the gamma-cyclodextrin and the crosslinking agent of tetrafluoroterephthalonitrile is 3:1:1, and the synthesis step comprises the steps of putting β -cyclodextrin, gamma-cyclodextrin, the crosslinking agent of tetrafluoroterephthalonitrile and a catalyst of sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of N, N-dimethylformamide to toluene is 8:1), wherein the mass ratio of β -cyclodextrin, gamma-cyclodextrin, the crosslinking agent of the catalyst of the mixed solvent of N, N-dimethylformamide and toluene is 0.08: 0.02:0.10:1, reacting for 30 hours at 105 ℃, filtering a reaction liquid after the reaction is finished, sequentially washing a filter cake with hydrochloric acid, water and isopropanol, and drying the filter cake to constant weight to obtain the polymerization cyclodextrin desulfurizer F.
Example 7
The polymerization cyclodextrin fine desulfurizer G consists of active components α -cyclodextrin, β -cyclodextrin, gamma-cyclodextrin and a crosslinking agent tetrafluoroterephthalonitrile, wherein the mass ratio of the active components α -cyclodextrin, β -cyclodextrin, gamma-cyclodextrin and the crosslinking agent tetrafluoroterephthalonitrile is 1:1:1:1, the synthesis step comprises the steps of placing the active components α -cyclodextrin, β -cyclodextrin, gamma-cyclodextrin, the crosslinking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene (the volume ratio of N, N-dimethylformamide to toluene is 8:1), wherein the mass ratio of the mixed solvent of α -cyclodextrin, β -cyclodextrin, gamma-cyclodextrin, the crosslinking agent, the catalyst, N-dimethylformamide and toluene is 0.03: 0.01:0.04:1, reacting for 40 hours at 95 ℃, filtering a reaction liquid after the reaction is finished, sequentially washing the reaction liquid with hydrochloric acid, water and isopropanol to obtain a constant weight filter cake, and freezing and drying the polymerization cyclodextrin G to obtain the polymerization heavy desulfurizer G.
The poly cyclodextrin desulfurizer A, C, D, F, G (sequentially marked as α -CDP, β -CDP, gamma-CDP, (β, gamma) -CDP, (α, gamma) -CDP) and dibenzothiophene (initial sulfur concentration is 100 mu g)-1) The light oil product is mixed according to the mass ratio of the oil to the solvent at normal pressure and is desulfurized for 90 minutes at 30 ℃. The effect of five kinds of polymeric cyclodextrin desulfurizers on the removal of dibenzothiophene is shown in figure 1. As can be seen from FIG. 1, the five polymeric cyclodextrin desulfurizers all exhibit excellent removal effects on dibenzothiophene.
The polymeric cyclodextrin desulfurizer C (β -CDP) and the mixture containing different sulfides (initial sulfur concentration is 100 mug. g)-1) The light oil product is mixed at normal pressure according to the mass ratio of the oil to the solvent of 1:40, and is desulfurized for 90 minutes at the temperature of 30 ℃, the desulfurization effect is shown in figure 2, and 1-7 sulfides in the figure 2 are tert-butyl mercaptan, ethyl sulfide, diethyl disulfide, thiophene, thiophenol, benzothiophene and dibenzothiophene in sequence. As can be seen from FIG. 2, the cyclodextrin polymeric desulfurizer C shows desulfurization effect on 7 different types of sulfides, and especially shows more excellent removal effect on sulfides containing aromatic ring structures.
Comparative examples
The polymerized cyclodextrin desulfurizer C (β -CDP) or β -CD or active carbon and dibenzothiophene (initial sulfur concentration is 100 mu g)-1) The light oil product is mixed according to the mass ratio of the oil to the agent at normal pressure of 1:40, the desulfurization is carried out for 90 minutes at 30 ℃, and the desulfurization effect is shown in figure 3. As can be seen from figure 3, the desulfurizer C of the invention has obvious desulfurization effect improvement compared with the active component β -CD, and simultaneously has excellent desulfurization effect compared with active carbon, which shows that the desulfurizer of the invention has ingenious design and synthesis and more obvious desulfurization performance.
It is obvious that the above examples are only examples for clearly illustrating the invention and are not intended to limit the embodiments of the polymeric cyclodextrin desulfurization agent for desulfurization of light oils according to the invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. All embodiments need not be, and cannot be, enumerated here. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (1)
1. The application of the polymerized cyclodextrin fine desulfurizer for removing different types of sulfides in light oil is characterized in that the polymerized cyclodextrin fine desulfurizer consists of one or a compound of active components α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin and a crosslinking agent tetrafluoroterephthalonitrile, and the polymerized cyclodextrin fine desulfurizer is synthesized by the following steps of putting active components α -cyclodextrin, β -cyclodextrin and gamma-cyclodextrin into or a compound of active components, putting a crosslinking agent tetrafluoroterephthalonitrile and a catalyst sodium carbonate into a mixed solvent of N, N-dimethylformamide and toluene, reacting for 24-48 hours at 90-110 ℃, filtering a reaction solution after the reaction is finished, sequentially washing a filter cake by hydrochloric acid, water and isopropanol, and freeze-drying to constant weight to obtain the polymerized cyclodextrin fine desulfurizer, wherein the volume ratio of the N, N-dimethylformamide to the toluene is 8:1, the mass ratio of the active components to the crosslinking agent is 5-0.5:1, the mass of the catalyst is the sum of the mass of the active components and the crosslinking agent, and the total mass ratio of the active components to the crosslinking agent to the toluene is 0.05-0.05.
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