CN114181734A - Deep desulfurization method for coupling catalytic oxidation-adsorption of white oil and transformer oil by utilizing high-adsorption-capacity adsorbent - Google Patents
Deep desulfurization method for coupling catalytic oxidation-adsorption of white oil and transformer oil by utilizing high-adsorption-capacity adsorbent Download PDFInfo
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 74
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 67
- 230000023556 desulfurization Effects 0.000 title claims abstract description 67
- 239000003463 adsorbent Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 52
- 230000008878 coupling Effects 0.000 title claims abstract description 17
- 238000010168 coupling process Methods 0.000 title claims abstract description 17
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 59
- 239000011593 sulfur Substances 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims description 33
- 239000007800 oxidant agent Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 150000002432 hydroperoxides Chemical group 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XRXANEMIFVRKLN-UHFFFAOYSA-N 2-hydroperoxy-2-methylbutane Chemical compound CCC(C)(C)OO XRXANEMIFVRKLN-UHFFFAOYSA-N 0.000 claims description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 5
- 150000003568 thioethers Chemical class 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 150000003464 sulfur compounds Chemical class 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 3
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- 238000004088 simulation Methods 0.000 claims description 3
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- 230000004913 activation Effects 0.000 claims description 2
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 71
- 238000011069 regeneration method Methods 0.000 abstract description 16
- 230000008929 regeneration Effects 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract 2
- 150000003457 sulfones Chemical class 0.000 abstract 2
- 150000003462 sulfoxides Chemical class 0.000 abstract 2
- 150000002978 peroxides Chemical class 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 112
- 239000000047 product Substances 0.000 description 32
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 19
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- 238000007254 oxidation reaction Methods 0.000 description 18
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- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 8
- 238000010828 elution Methods 0.000 description 7
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- -1 molybdic acid peroxide Chemical class 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001741 organic sulfur group Chemical group 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 241000783428 Achillea wilsoniana Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000003710 cerebral cortex Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 239000000084 colloidal system Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
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- 239000000284 extract Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000000653 nervous system Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000007436 olfactory function Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
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- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
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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
- 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
- C10G53/14—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one oxidation step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/14—Diatomaceous earth
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/12—Electrical isolation oil
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/14—White oil, eating oil
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a deep desulfurization method for coupling white oil and transformer oil through catalytic oxidation-adsorption by using an adsorbent with high adsorption capacity. Sulfur-containing compounds in white oil and transformer oil are efficiently catalytically oxidized into high-polarity sulfonic acid, sulfoxide or sulfone substances through a Ti-loaded diatomite adsorbent material and peroxide, and then the high-polarity sulfonic acid, sulfoxide or sulfone substances can be adsorbed on the surface of the adsorbent material with high selectivity, white oil and transformer oil with the sulfur content of 0.2-200 mug/g can be efficiently and deeply desulfurized, the sulfur content can be removed to the ng/g level, and the desulfurization rate can exceed 99%. The method is suitable for deep desulfurization of white oil and transformer oil, and has the advantages of simplicity, high efficiency, low investment, mild reaction conditions, easy regeneration of the adsorbent and the like.
Description
Technical Field
The invention belongs to the field of deep desulfurization of white oil and transformer oil, and particularly relates to a method for oxidizing sulfur-containing compounds in the white oil and the transformer oil by taking organic hydroperoxide as an oxidant under the coupling action of an oxidation catalyst and an adsorbent, and then adsorbing and removing the sulfur-containing compounds by the adsorbent in a high-selectivity manner.
Technical Field
The hazards of sulfur-containing compounds in white oils, transformer oils are well known: (1) thiols and thioethers of lower molecular weight have pungent malodorous odors that act on the human olfactory senses to stimulate the nervous system and the regulatory dysfunction of the cerebral cortex, which over time can lose olfactory function. Mercaptan is an active sulfide, can cause the formation of colloid and precipitation of oil products, influences the stability of the oil products, and is an acidic substance which has a strong corrosion effect on metal equipment. But the presence of sulfur-containing compounds will also cause the process catalyst to be poisoned and fail. (2) Dibenzyl disulfide (DBDS), which is an antioxidant to improve transformer oil quality, is believed to be a major substance responsible for corrosion of transformer copper wire and reacts with copper at high temperatures to form semi-conductive cuprous sulfide (Cu)2S) precipitation. Cu2S migrates to the insulating paper and insulating oil due to weak adhesive force after being generated on the surface of the copper conductor, so that the electrical performance of an oil-paper insulating system is seriously reduced, and finally transformer equipment is seriously damaged, and the accident rate caused by DBDS is up to 90%.
When the white oil is applied to cosmetics, if sulfides are contained in the white oil, the quality of the cosmetics is affected, and adverse effects on the aspects of the odor, the color and the like of the cosmetics or foods can be caused; especially as coating/diluting agent of essence, etc., wherein trace amount of sulfide can cause odor type change. Therefore, in the fields of cosmetics, foods and the like, the sulfur content of white oil is strictly required, and the conventional desulfurization method is difficult to achieve.
In recent years, as noble metal catalysts or adsorbents are protected, the product quality is improved, national calls and policies are actively responded, and environmental pollution is reduced, the requirement on sulfide removal precision is higher and higher, and the hydrodesulfurization technology with harsh production conditions (high temperature of 300-400 ℃ and high pressure of 3-7 MPa) cannot meet the requirement of the future era. In the field of deep desulfurization, scholars at home and abroad always explore and develop new technologies.
CN1554730A provides a catalytic oxidation method for deeply removing sulfur-containing compounds in oil products, which adopts a solid titanium-containing molecular sieve as a catalyst and hydrogen peroxide as an oxidant to oxidize the sulfur-containing compounds in the oil products at 40-80 ℃ and normal pressure, extracts and removes the oxidized products by using methanol, acetonitrile, tert-butyl alcohol, water or other mixtures as solvents, and can remove 80-90% of the sulfur-containing compounds in the oil products by separation. The patent carries out extraction and removal on the oxidation product, the consumption of an extraction solvent is large, a certain solubility exists between an oil product and the extraction solvent, the separation is difficult, the solvent recovery cost is high, and the requirement on the operation environment is high; the adopted oxidant is 30 wt.% of hydrogen peroxide, the oil-water two-phase reaction effect is poor, and simultaneously, water can be introduced into the oil product.
CN105602609A provides a catalytic oxidation desulfurization method based on molybdic acid peroxide ionic liquid, which comprises the following steps: taking molybdic acid peroxide ionic liquid as a catalyst, stirring the molybdic acid peroxide ionic liquid with an oxidant, an extractant and simulated gasoline for 5 to 30min under the conditions of normal pressure and reaction temperature of between 30 and 50 ℃ for full reaction, standing the mixture for 5min after the reaction, and taking the upper layer after two-phase separation to obtain the desulfurized oil product. The ionic liquid catalytic system has unique catalytic activity in the aspect of oxidative desulfurization, but has the defects of large dosage of ionic liquid, difficult separation and purification of the catalytic system and products and the like, so the practical application is greatly limited.
CN110523370A provides a preparation method of an adsorbent for removing dibenzyl disulfide from transformer oil at normal temperature, and particularly discloses that the adsorbent comprises a porous carrier and silver nitrate loaded on the porous carrier, wherein the adsorbent utilizes Pearson Hardney and Achillea Wilsoniana, and the surface of the carrier is loaded with soft acid anions which have adsorption effect on DBDS. That is, this patent is directed to a soft base DBDS to solve the problem of adsorption and desorption of the soft base DBDS, and does not suggest oxidizing the soft base DBDS to obtain a hard base having a strong polarity.
Compared with the traditional adsorbent which has poor direct adsorption effect and large adsorbent consumption, the method for removing the sulfur-containing compounds in the white oil and the transformer oil by adopting catalytic oxidation-adsorption coupling has the advantages of simplicity, high efficiency, depth, small investment, mild reaction conditions, easy regeneration of the adsorbent and the like, and has good industrial application prospect.
The existing adsorbent comprises Ti loaded on a carrier material with adsorption performance as an adsorption material, and the currently adopted carrier is generally silica gel, a zeolite molecular sieve, clay and the like, wherein the content of Ti is relatively high, the content of Ti is mostly more than 10%, the cost is high, and the adsorption capacity of the adsorbent is low.
Disclosure of Invention
In view of the above, the primary object of the present invention is to provide a deep desulfurization method for white oil and transformer oil by catalytic oxidation-adsorption coupling with high adsorption capacity adsorbent, which only uses a small amount of TiO supported2The high-adsorption-capacity adsorbent which can achieve a better adsorption desulfurization effect can be used for efficiently and deeply desulfurizing white oil and transformer oil systems with different sulfur contents of 0.2-200 mu g/g, the sulfur content can be removed to ng/g level, the desulfurization rate can exceed 98%, and the material can be regenerated and recycled.
The application provides a deep desulfurization method for coupling white oil and transformer oil by catalytic oxidation-adsorption with a high adsorption capacity adsorbent, which comprises the following steps:
(1) weighing an oil product to be detected containing a sulfur compound, and adding the oil product to be detected into a reaction tube, wherein the oil product to be detected comprises at least one of white oil, transformer oil or simulation oil;
(2) adding the prepared adsorbent into the oil product to be detected in the step (1), wherein the adsorbent comprises diatomite and an active component TiO loaded on the diatomite2The active component Ti accounts for 0.2-2.5% of the mass percent of the adsorbent, and the mass ratio of the adsorbent to the oil product to be detected is as follows: (0.9-1.1) to 100;
(3) adding an oxidant into the oil product to be detected in the step (1), wherein the oxidant is organic hydroperoxide;
(4) mixing the oil product to be detected, an oxidant and an adsorbent, and stirring at a preset temperature for a preset time to perform catalytic oxidation-adsorption reaction; preferably, the preset temperature is 30 ℃ and the preset time is 2 hours.
(5) And (4) after the catalytic oxidation-adsorption reaction is finished, carrying out solid-liquid separation on the mixture to obtain the desulfurized and purified oil product.
The white oil is the mixture of refined liquid hydrocarbon obtained from petroleum, mainly the mixture of saturated cyclane and paraffin, and the crude oil is obtained by normal pressure and reduced pressure fractionation, solvent extraction and dewaxing, and hydrorefining. The application aims at the research of the deep desulfurization efficiency of the adsorbent loaded with Ti, the carrier of which is diatomite, on white oil and transformer oil, and adopts the diatomite adsorbent with low Ti content to carry out deep desulfurization on the white oil and the transformer oil. For the adsorbent loaded with Ti, the carrier of which is silica gel, zeolite molecular sieve or clay, the higher the Ti content is, the better the desulfurization effect is, the application finds that, for the carrier of which is diatomite, the better the desulfurization effect is when the active component Ti accounts for 0.2-2.5% of the mass of the adsorbent than the desulfurization effect when the mass is more than 4%, and especially when the active component Ti accounts for 0.2% or 2.5% of the mass of the adsorbent, the best deep desulfurization effect is achieved.
Preferably, in step (1), the simulated oil is n-dodecane or a saturated mixture of cycloalkanes and paraffins.
Preferably, in step (1), the sulfur-containing compound in the oil to be tested includes at least one of thiol, thioether and disulfide.
Preferably, in the step (1), the sulfur content in the oil product to be detected is 0.2 to 200 mu g/g.
Preferably, the mass percentage of the Ti in the diatomite is 0.2% or 2.5%.
Preferably, the adsorbent is prepared by a quantitative impregnation method and is obtained after activation for 4 hours at 550 ℃.
Preferably, in the step (3), the organic hydroperoxide includes at least one of cumene hydroperoxide, tert-amyl hydroperoxide or tert-butyl hydroperoxide.
Preferably, in the step (3), the molar ratio of the organic hydroperoxide to the sulfur in the oil product is (2-5) to (1-2).
Preferably, the adsorbent material is prepared by loading a precursor of Ti on a diatomite material, and calcining a mixture of the precursor and the diatomite material to obtain the adsorbent material, wherein the TiO is2The method for loading the precursor on the diatomite material comprises an impregnation method, a mechanical mixing method, a sol-gel method and a chemical precipitation method, wherein the calcination method comprises the steps of heating to 400-550 ℃ at the heating rate of 1-5 ℃/min in the air atmosphere, and the calcination time is 3.5-5.5 h; the hot air oxidation regeneration method is the same as the method of calcination in the preparation of the material.
The application also provides the purified white oil and the transformer oil obtained by desulfurization by adopting the catalytic oxidation-adsorption coupling white oil and transformer oil deep desulfurization method.
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention adopts the catalytic adsorption dual-function material and only uses a small amount of TiO2Loaded on diatomite, can efficiently remove sulfur-containing compounds such as mercaptan, thioether, disulfide and the like in white oil and transformer oil systems, has the desulfurization rate of over 98.0 percent, can meet the requirement of deep removal of the sulfur-containing compounds in the white oil and the transformer oil, and only uses TiO loaded with 0.2 to 2.5 percent2The desulfurization rate of the adsorbent can reach more than 98 percent, and the adsorbent has higher desulfurization adsorption capacity;
(2) the invention adopts the catalytic adsorption dual-function material, adds the organic oxidant, can avoid oil-water two-phase reaction, can better disperse in the white oil and the transformer oil than the inorganic oxidant, has higher oxidizing property and is not enough to oxidize the main components of the white oil and the transformer oil;
(3) the proper proportion of the oxidant, the sulfur-containing compounds in the white oil and the transformer oil and the catalytic adsorption dual-function material can remove the sulfur-containing compounds in the white oil and the transformer oil more efficiently, when the material or the oxidant is insufficient, the catalytic oxidation and the adsorption of the material can be saturated, so that the aim of effectively removing the sulfur-containing compounds in the white oil and the transformer oil can not be fulfilled, and if the material or the oxidant is excessive, the action of the material and the oxidant can not be effectively utilized, so that the cost is increased;
(4) the catalytic oxidation-adsorption coupling desulfurization method provided by the invention adopts a catalytic adsorption dual-function material, has two functions of catalysis and adsorption, is synchronously carried out in the catalytic oxidation and adsorption processes at normal temperature and normal pressure, uses a small amount of oxidant to oxidize sulfur-containing compounds in white oil and transformer oil under the action of catalytic active sites of the material, generates oxidation products with higher polarity, and is simultaneously oxidized by a small amount of TiO2The adsorption sites (Si-OH) of the adsorbent material are subjected to high-selectivity adsorption, and then the adsorbent material is subjected to solid-liquid separation with the white oil and the transformer oil, so that the aim of high-selectivity deep desulfurization is fulfilled; the process is simple and efficient, the energy consumption is low, and the hydrogen consumption is zero; and the material can be regenerated and recycled, has lower cost and is beneficial to environmental protection, thereby having good industrial application prospect.
Drawings
FIG. 1 is a graph of the dynamic desulfurization profile of real transformer oil with different sulfur (as sulfur in dibenzyl disulfide) content.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
(1) Preparation of the adsorbent
The adsorbent material used in the following examples was prepared by reacting TiO2The precursor is loaded on a diatomite material, and then the adsorbent material is obtained by calcining the material loaded with the precursor, wherein the method for loading the precursor on the diatomite material comprises an impregnation method, a mechanical mixing method, a sol-gel method and a chemical precipitation method.
(2) Deep desulfurization method for white oil and transformer oil by utilizing high adsorption capacity catalytic oxidation-adsorption coupling
Step (1): weighing an oil product to be detected containing a sulfur compound, and adding the oil product to be detected into a reaction tube, wherein the oil product to be detected comprises one of white oil, transformer oil or simulation oil;
step (2): adding the prepared adsorbent into the oil product to be detected in the step (1), wherein the adsorbent comprises kieselguhr and TiO loaded on the kieselguhr2The mass percentage of Ti in the adsorbent is 0.2% -2.5% (specifically, the mass ratio of the adsorbent to the oil product to be measured is as follows in tables 1 to 3): 1: 100;
and (3): adding an oxidant into the oil product to be detected in the step (1), wherein the oxidant is organic hydroperoxide;
and (4): mixing an oil product to be detected, an oxidant and an adsorbent, and stirring at a preset temperature for a preset time to perform catalytic oxidation-adsorption reaction; preferably, the preset temperature is 30 ℃ and the preset time is 2 hours.
(5): after the catalytic oxidation-adsorption reaction in the step (4) is completed, the mixture is subjected to solid-liquid separation operation to obtain a desulfurized and purified oil product, and the sulfur content is detected by using a JF-TS-5000 type sulfur detector.
The removal performance of the materials for organic sulfur was examined according to the above method under the conditions of different adsorbent materials, different metal loadings, white oil and transformer oil systems with different sulfur contents, and different amounts of oxidant (see table 1), and it can be seen from the following specific examples, and the specific desulfurization performance results are shown in tables 1-2. As shown in table 1, the Ti loading was: 0.2-10%; the sulfur-containing compounds selected from the white oil are Propanethiol (PM) and methyl sulfide (DMS), and the sulfur-containing compounds selected from the transformer oil are dibenzyl disulfide (DBDS); the sulfur content is 0.2-200 mu g/g, the molar ratio of the oxidant to the sulfur in the sulfur-containing hydrocarbon is (1.0-5.0): 1, and the mass ratio of the adsorbent material to the sulfur-containing hydrocarbon is 1: 100. The oxidant in tables 1 and 2 was TAHP.
Preparation of Ti-diatomite adsorbent
(1) Preparation of Ti-diatomite: weighing 1.0g of dried diatomite material, adding into 46mL of ethanol, and magnetically stirring to uniformly disperse in the ethanol; dissolving 114 mu L of tetraethyl titanate in 4mL of ethanol, shaking to uniformly disperse the tetraethyl titanate, dropwise adding the tetraethyl titanate into ethanol dispersion liquid of the diatomite carrier, stirring for 2 hours, removing the ethanol on a rotary vacuum evaporator, drying in a drying oven at constant temperature of 100 ℃, heating to 550 ℃ in a muffle furnace at the heating rate of 5 ℃/min, calcining for 4 hours, and naturally cooling to room temperature to obtain the 2.5 percent Ti-diatomite material. The adsorbents of each of the different Ti loadings in tables 1 and 2 can be obtained by adjusting the amount of tetraethyl titanate.
(2) The experimental conditions are as follows: simulated white oils include n-dodecane and propanethiol; the sulfide in the real white oil or the transformer oil is propanethiol; the sulfur content was 200. mu.g/g (see tables 1 and 2 for sulfur content in specific examples and comparative examples), and the molar ratio of the oxidizing agent to sulfur in the sulfur-containing hydrocarbon was 5:1 (see tables 1 and 2 for molar ratio of the oxidizing agent to sulfur in examples and comparative examples).
Comparative analysis
To illustrate the superiority of the present invention, a variable analysis was also performed based on example 1, and the following comparative examples were made.
TABLE 1 Effect of removing Sulfur-containing Compounds from simulated white oil and Transformer oil under different conditions
And (3) analysis: as can be seen from examples 1-3 of Table 1, the catalytic oxidation-adsorption total sulfur removal rate of the low titanium-loading diatomite molecular sieve material on 3 sulfur-containing compounds, namely, propyl mercaptan, methyl sulfide and dibenzyl disulfide, exceeds 90%. From comparative examples 1-3, it can be seen that the removal rate of sulfur-containing compounds by simple adsorption of the titanium-free diatomite molecular sieve material is low (less than 15%), which indicates that the selectivity of sulfur-containing compounds by simple physical adsorption is low. As can be seen from examples 1-3 and comparative examples 1-5, the oxidation-adsorption desulfurization rate of the Ti-free diatomite molecular sieve material is lower than that of the catalytic oxidationThe total adsorption sulfur removal rate indicates that the process needs both the catalysis of Ti and the participation of an oxidant, namely, a catalytic site and the oxidant are matched for use to successfully carry out the desulfurization. It is worth mentioning that the oxidation-adsorption desulfurization rate is higher than the simple adsorption desulfurization rate (comparative example 4 and comparative example 3), which is probably due to the trace amount of aluminum or iron (Al) contained in the diatomaceous earth molecular sieve material2O3：0.04％，Fe2O3: 0.01 percent) and has certain catalytic action on oxidation reaction.
From examples 4-13, it can be seen that under different reaction conditions or systems, the material performs catalytic oxidation-adsorption on the sulfur-containing compound, and from the point of view of the total sulfur removal rate, in simulated white oil and transformer oil systems with different sulfur contents, the catalytic oxidation-adsorption desulfurization performance of the catalytic adsorption dual-function material with a certain oxidant addition amount and a certain metal loading amount is excellent, which indicates that the material catalytic oxidation-adsorption desulfurization method has a wide application range. As can be seen from examples 15-16 and comparative example 8, the selectivity and removal rate of sulfur-containing compounds by pure physical adsorption of the carrier is low. Different carrier materials are adopted to remove the sulfur-containing compounds with different rates, namely, the oxidation products of the sulfur-containing compounds need the adsorption sites of the materials to carry out high-selectivity adsorption removal.
The desulfurization effect of the Ti-diatomaceous earth adsorptive power using diatomaceous earth as a carrier is better in comparative example 6 and comparative example 7, and comparative example 9 than in example 3.
From comparative examples 10 to 12 as compared with example 2, and from comparative examples 14 to 16 as compared with example 3, it was found that when the TI loading was higher than 4%, the desulfurization rate effect was rather poor, and that the desulfurization rate effect was better with a small TI loading. Comparative example 13 is compared with example 2, and comparative example 17 is compared with example 3, it can be found that when the TI loading is less than 0.2%, the desulfurization efficiency effect is not good, which indicates that the TI loading in the present invention has a better desulfurization effect only at 0.2% -2.5%, and the results of the present experimental data prove that the effect is outstanding in this range.
In view of the fact that the catalytic oxidation adsorption coupling desulfurization method has excellent desulfurization performance in a simulated white oil and transformer oil system, the process of removing sulfur-containing compounds in real white oil and transformer oil by catalytic oxidation-adsorption coupling is carried out:
TABLE 2 Effect of removing sulfur compounds from real white oil and transformer oil under different conditions
And (3) analysis: from examples 14 to 22 in table 2, it can be seen that, when titanium-diatomite materials with different metal titanium loadings are applied to real white oil and transformer oil systems with different sulfur contents to perform catalytic oxidation-adsorption coupling desulfurization processes under the conditions of different oxygen-sulfur ratios and different oxidant amounts, the desulfurization rates are all higher, and from comparative example 18 to comparative example 21, it can be found that the influence of the carrier on the desulfurization rates is larger, and the desulfurization effect of the Ti-diatomite adsorption force with the carrier being diatomite is better. Comparative example 22-comparative example 25 compared to example 17, and comparative example 26-comparative example 29 compared to example 21 the low Ti loading sorbents of the present application have a superior desulfurization effect with high sorption capacity.
And carrying out a fixed bed dynamic experiment on the real transformer oil: mixing an oxidant TAHP and the organic sulfur in the real transformer oil at a molar ratio of 5 at 30 ℃ in a storage tank to obtain real transformer oil containing TAHP; pumping into an adsorption column filled with the Ti-diatomite material as in example 3, and performing catalytic oxidation-adsorption coupling desulfurization; the used Ti-diatomite material is regenerated by adopting a solvent elution and hot air oxidation method, and the fixed bed layer of the catalytic adsorption material can be recycled. As shown in figure 1, wherein the abscissa in figure 1 represents the treated oil amount per gram of adsorbent material, and the ordinate represents the sulfur content in the oil at the outflow end of the fixed bed at the corresponding treatment amount, the process can treat the sulfur content of 10, 50 and 150 mug/g of real transformer oil to be less than 0.2 mug/g, and the adsorption desulfurization treatment amount of the material can reach 210, 530 and 2050L-oil/kg-material at the penetration concentration of 10, 10 and 1 mug/g, so as to meet the requirements of deep desulfurization and high treatment amount.
(3) Determination of the Cyclic regeneration Performance of the adsorbent Material
The adsorbent materials of examples 1-3 were subjected to solvent elution regeneration: washing the used adsorbing material for 1h by using an ethanol solvent; then filtering and washing with solvent at the same time; the filter cake obtained was then dried in a constant temperature oven at 100 ℃ for at least 4h, followed by the next desulfurization-regeneration cycle experiment. The solvent is regenerated for 5 times by hot air oxidation method, which is based on the principle of oxidizing and decomposing sulfide attached to the surface of the material to generate CO2、SO2And H2And the gas-state small molecules such as O and the like escape from the pore or the surface of the material surface, and the adsorption sites are recovered. When regenerating by the hot air oxidation method, firstly, filtering the used material and washing the used material with a proper amount of dodecane at the same time; and then placing the obtained filter cake in a muffle furnace, heating to 100 ℃ at a heating rate of 10 ℃/min, keeping for 2h, then heating to 550 ℃ at a heating rate of 5 ℃/min, keeping for 4h, and finally cooling to 100 ℃ to wait for the next desulfurization-regeneration cycle experiment.
The regenerated materials obtained by the above-mentioned regeneration in examples 1 to 3 were recycled and added to the same system as before for adsorption desulfurization, and the desulfurization effect data measured finally are shown in Table 3.
TABLE 3 solvent elution regeneration cycle performance of adsorbent materials
As can be seen from table 3, the regeneration cycle performance of the adsorbent material by the solvent elution method, in example 1, the adsorbent material cannot be completely regenerated by the solvent elution method, and it can be seen that after 2 adsorption-regeneration cycles, the desulfurization performance of the material is reduced to about 50% of the performance of the fresh material; for examples 2-3, the solvent elution method can basically remove the sulfur-containing compounds adsorbed on the surface of the material by elution, so that the catalytic and adsorption sites of the material are exposed, and the desulfurization performance is recovered. It can be seen that after 4 adsorption-regeneration cycles, the desulfurization performance of the material was substantially restored to the level of the fresh material.
TABLE 4 Hot air Oxidation regeneration cycling Performance of adsorbent materials
From table 4 the hot air oxidation regeneration cycle performance of the sorbent materials, it can be seen that for examples 1-3, i.e., for the 3 sulfide systems described above, the hot air oxidation process can regenerate the material, expose the catalytic and adsorption sites of the material, and recover the desulfurization performance. It can be seen that after 4 adsorption-regeneration cycles, the desulfurization performance of the material was substantially restored to the level of the fresh material. Therefore, the adsorbent material has better renewable cycle performance, and the requirement of complete regeneration cycle can be met by adopting a hot air oxidation method.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A deep desulfurization method for coupling white oil and transformer oil by catalytic oxidation-adsorption with an adsorbent with high adsorption capacity is characterized by comprising the following steps:
(1) weighing an oil product to be detected containing a sulfur compound, and adding the oil product to be detected into a reaction tube, wherein the oil product to be detected comprises at least one of white oil, transformer oil or simulation oil;
(2) adding the prepared adsorbent into the oil product to be detected in the step (1), wherein the adsorbent comprises diatomite and an active component TiO loaded on the diatomite2The mass percentage of Ti in the diatomite is 0.2-2.5 percentThe mass ratio of the adsorbent to the oil to be detected is as follows: (0.9-1.1) to 100;
(3) adding an oxidant into the oil product to be detected in the step (1), wherein the oxidant is organic hydroperoxide;
(4) mixing the oil product to be detected, an oxidant and an adsorbent, and stirring at a preset temperature for a preset time to perform catalytic oxidation-adsorption reaction;
(5) and (4) after the catalytic oxidation-adsorption reaction is finished, carrying out solid-liquid separation on the mixture to obtain the desulfurized and purified oil product.
2. The catalytic oxidation-adsorption coupled process for deep desulfurization of white oil and transformer oil according to claim 1, wherein in step (1), the simulated oil is n-dodecane or a mixture of saturated naphthenic hydrocarbons and paraffinic hydrocarbons.
3. The catalytic oxidation-adsorption coupled method for deeply desulfurizing white oil and transformer oil according to claim 1, wherein in step (1), the sulfur-containing compound in the oil to be tested comprises one or more of thiol, thioether and disulfide.
4. The catalytic oxidation-adsorption coupling white oil and transformer oil deep desulfurization method according to claim 1, wherein in the step (1), the sulfur content in the oil product to be tested is 0.2 μ g/g-200 μ g/g.
5. The method for deep desulfurization of white oil and transformer oil coupled with catalytic oxidation-adsorption according to claim 1, wherein the mass percentage of Ti in the diatomite is 0.2%.
6. The method for deep desulfurization of white oil and transformer oil coupled with catalytic oxidation-adsorption according to claim 1, wherein the mass percentage of Ti in the diatomite is 2.5%.
7. The catalytic oxidation-adsorption coupling white oil and transformer oil deep desulfurization method as claimed in claim 1, wherein the adsorbent is prepared by a quantitative impregnation method and is obtained after activation for 4h at 550 ℃.
8. The catalytic oxidation-adsorption coupled deep desulfurization method for white oil and transformer oil according to claim 1, wherein in the step (3), the organic hydroperoxide comprises more than one of cumene hydroperoxide, tert-amyl hydroperoxide or tert-butyl hydroperoxide.
9. The catalytic oxidation-adsorption coupled deep desulfurization method for white oil and transformer oil according to claim 1, wherein in the step (3), the molar ratio of the organic hydroperoxide to the sulfur in the oil product is (2-5) to (1-2).
10. A purified white oil or transformer oil desulfurized by a catalytic oxidation-adsorption coupling white oil or transformer oil deep desulfurization method according to any one of claims 1 to 9.
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