CN115161072A - Method for oxidizing, extracting and desulfurizing wax oil in microchannel reactor - Google Patents
Method for oxidizing, extracting and desulfurizing wax oil in microchannel reactor Download PDFInfo
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- CN115161072A CN115161072A CN202210765759.3A CN202210765759A CN115161072A CN 115161072 A CN115161072 A CN 115161072A CN 202210765759 A CN202210765759 A CN 202210765759A CN 115161072 A CN115161072 A CN 115161072A
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 53
- 230000003009 desulfurizing effect Effects 0.000 title abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 104
- 239000011593 sulfur Substances 0.000 claims abstract description 104
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000002156 mixing Methods 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 44
- 230000023556 desulfurization Effects 0.000 claims abstract description 44
- 239000007800 oxidant agent Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000005191 phase separation Methods 0.000 claims abstract description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 122
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 6
- 238000005728 strengthening Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 84
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 81
- 230000001105 regulatory effect Effects 0.000 description 68
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 57
- 229960000583 acetic acid Drugs 0.000 description 39
- 239000012362 glacial acetic acid Substances 0.000 description 35
- 239000012071 phase Substances 0.000 description 22
- 239000012528 membrane Substances 0.000 description 9
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010762 marine fuel oil Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010747 number 6 fuel oil Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 phosphotungstate Chemical compound 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention provides a method for oxidizing, extracting and desulfurizing wax oil in a microchannel reactor, which comprises the steps of mixing the wax oil and an oxidation reaction catalyst in a first micro mixer to realize the full contact of the wax oil and the catalyst, then mixing the mixture of the wax oil and the oxidation catalyst and an oxidant in a second micro mixer, and then reacting through the microchannel reactor for 10-100min; and finally, after the reaction, enabling the material flow to pass through phase separation equipment, fractionating a water phase to obtain a reaction catalyst for recycling, mixing an oil phase and an extracting agent in a third micro mixer, removing most of oxidation products of sulfur-containing components in the wax oil, and then carrying out phase separation to obtain the desulfurized wax oil. Compared with the prior art of oxidative desulfurization of wax oil, the method has the advantages that the miniaturization of equipment is realized by strengthening the desulfurization process by using the micro-mixer and the micro-channel reactor, the use amounts of the catalyst and the oxidant are reduced, the process is simple, the continuous production can be realized, and the method has wide actual industrial application prospect.
Description
Technical Field
The invention relates to a method for oxidative extraction and desulfurization of wax oil in a microchannel reactor, belonging to the field of oil product desulfurization.
Background
In recent years, with the rapid development of the world economy, the maritime trade becomes more busy, resulting in the increasing demand for bunker fuel oil. Meanwhile, as the international maritime organization requires that the sulfur content of the marine fuel oil is reduced from 3.5 percent to 0.5 percent by 2020, the marine oil producer is provided with new challenges. The low-sulfur diesel oil components and the like are directly used, so that the viscosity is low, the power is insufficient, the cost is high, and the low-price wax oil, heavy oil and the like need to be blended to improve the viscosity and reduce the cost.
The sulfur content of the wax oil which can be used for blending and producing low-sulfur marine fuel oil in the current refinery reaches up to 1% -3%, the wax oil is directly used for blending and adding with lower proportion, and the cost is not obviously reduced. The current solution is to mix high sulfur components such as wax oil, residual oil, etc. for hydrotreating, and remove the sulfur components therefrom for blending low sulfur bunker fuel oil. But the hydrodesulfurization technology has harsh technological conditions, needs larger equipment investment and higher desulfurization cost, and the hydrogenated wax oil has smaller competitiveness when being used for producing low-sulfur marine fuel oil.
The oxidation extraction desulfurization technology is a technology capable of replacing hydrodesulfurization, and the basic principle of the technology is that sulfides in oil products are oxidized into sulfur oxides with strong polarity such as sulfones and the like by an oxidizing agent under the action of a catalyst, and the sulfur oxides have more polarity than the sulfides due to the fact that the electronegativity of oxygen is higher than that of sulfur, and are easily extracted and removed by a polar solvent, so that the sulfur content in the oil products is reduced. The oxidation desulfurization technology has simple process, mild condition and low equipment investment. However, most of the current reports on the wax oil oxidation extraction desulfurization technology are principle exploration, and few reports are provided for the novel process. The reported catalysts comprise formic acid, acetic acid, phosphotungstate and the like, and the oxidizing agent comprises hydrogen peroxide, peracetic acid, tert-butyl peroxide and the like, and the systems have the problems of low single-pass desulfurization rate, long reaction time, large using amount of the catalyst and the oxidizing agent and the like.
The existing wax oil oxidation desulfurization process adopts an intermittent stirred tank reaction process (CN 104593056A), has the defects of poor multiphase material mixing effect, poor mass transfer performance and the like, and the oxidative desulfurization effect of hydrogen peroxide/acetic anhydride on the coking wax oil shows that a hydrogen peroxide/acetic acid system is used for reacting for 75min in a stirred tank, and the desulfurization rate is only 55%. Meanwhile, as the oxidant is hydrogen peroxide (CN 102408915A, CN 105176570A), the oxidant is easy to decompose when being heated, and excessive addition is needed to ensure the desulfurization effect, so that the method is not beneficial to industrial production. The invention provides a method for continuously operating a wax oil oxidation desulfurization process by using a microchannel reactor, which has high equipment safety and can effectively shorten the reaction time and the consumption of an oxidant.
Disclosure of Invention
The invention aims to provide a novel process and a novel method for strengthening the oxidation desulfurization process of wax oil by using a microchannel reactor aiming at the defects of the conventional wax oil oxidation extraction desulfurization technology, and realizes the continuous oxidation desulfurization of the wax oil with short retention time and small using amount of oxidant by utilizing the efficient mass transfer mixing characteristic of the microchannel reactor.
The invention provides a method for oxidizing and extracting wax oil in a microchannel reactor, which is a method for improving the existing oxidizing, extracting and desulfurizing process by adopting the microchannel reactor. The method comprises the steps of mixing wax oil and an oxidation reaction catalyst in a first micro mixer to realize the full contact of the wax oil and the catalyst, then mixing the mixture of the wax oil and the oxidation catalyst with an oxidant in a second micro mixer, and then reacting through a micro-channel reactor for 10-100min; and finally, after the reaction, enabling the material flow to pass through phase separation equipment, fractionating a water phase to obtain a reaction catalyst for recycling, mixing an oil phase and an extracting agent in a third micro mixer, removing most of oxidation products of sulfur-containing components in the wax oil, and then carrying out phase separation to obtain the desulfurized wax oil.
In the method provided by the invention, the system comprises a raw material bottle, a feeding pump, a micro mixer, a micro channel reactor, a temperature control device, a back pressure valve, a membrane separator, a fractionator and the like, wherein the outlet pressure of the micro channel reactor is controlled by the back pressure valve connected between the membrane separator and the micro channel reactor. The micro mixer and the micro channel reactor are both arranged in the temperature control device.
In the method provided by the invention, the reaction temperature is 50-90 ℃, the outlet pressure of the microchannel reactor is 400-600 kPa, the molar ratio of the catalyst to the sulfur is 2:1-20, the molar ratio of the oxidant to the sulfur is 10-20.
In the method provided by the invention, the sulfur content of the wax oil is 1-2.87%; the catalyst is acetic acid, formic acid and the like; the oxidant used was 30% hydrogen peroxide; the extractant used was an acetonitrile solution with 25% water content.
The micro-mixing channel in the micro-mixer has the equivalent diameter of 0.1-1mm and the length of 100-500mm, and the equivalent diameter of the micro-channel reactor is 2mm, and the length can be adjusted according to the reaction time.
The method of the invention strengthens liquid-liquid two-phase mass transfer, disperses the wax oil and the oxidant into liquid drops with tiny and uniform sizes, and has the advantages of short reaction time, fast interphase mass transfer, high single-pass desulfurization rate, less oxidant and catalyst consumption and continuous operation compared with the prior reaction kettle technology. The oxidative extraction desulfurization of the wax oil is carried out in the microchannel reactor, and the desulfurization rate of over 65 percent can be obtained in shorter residence time, which is far higher than 55 percent reported in the literature. Meanwhile, under the same desulfurization rate, the method needs less oxidant, catalyst and reaction time, and the whole process can be continuously carried out, thereby greatly improving the working efficiency. .
Drawings
FIG. 1 is a schematic flow chart of a method provided by the present invention. In the figure: 1 is a catalyst tank; 2 is an oxidant tank; 3 is a wax oil tank which contains a heating device; 4 is an extracting agent tank; 5 is a catalyst pump, 6 is an oxidant pump, 7 is a wax oil pump, 8 is an extractant pump, 11 is a catalyst reflux pump, and 14 is an extractant reflux pump; 9 is a first micro mixer, 10 is a second micro mixer, and 18 is a third micro mixer; 12 is a micro-channel reactor; 16 is a first membrane separation device, 20 is a second membrane separation device; 13 The system comprises a back pressure valve 19, a catalyst fractionating tank 15, an extractant fractionating tank 17 and a temperature control device 24.
Detailed Description
FIG. 1 shows a flow chart of the present invention. As can be seen from fig. 1, the fresh catalyst delivered from the catalyst tank 1 by the catalyst pump 5 is mixed with the recycled catalyst, then mixed with the oxidant delivered from the oxidant tank 2 by the oxidant pump 6 in the first micromixer 9, then mixed with the wax oil delivered from the wax oil tank 3 by the wax oil pump 7 in the second micromixer 10, reacted by the microchannel reactor 12, and then sent to the first membrane separator 16, the aqueous phase is sent to the catalyst fractionation tank 15 to remove the moisture in the catalyst, and the recycled catalyst is returned by the pump 11. The oil phase separated by the first membrane separator 16 is mixed with the extractant delivered by the extractant pump 8 from the extractant storage tank 4 by the third micro-mixer 18 and then delivered to the second membrane separator 20, the oil phase 15 is a desulfurized product, the extractant is mixed with a new extractant after passing through the extractant fractionating tank 17, and the material 23 is discharged as waste liquid. Wherein the wax oil storage tank is provided with a heating device, a second micro mixer 10, a micro-channel reactor 12, a back pressure valve 13 and a first membrane separator 16 are all arranged in a temperature control device 24.
In order to verify the effect of the invention, hydrogen peroxide containing 30% of hydrogen peroxide is used as an oxidant, glacial acetic acid is used as a catalyst, acetonitrile with 25% of water content is used as an extractant, and the process flow of figure 1 is adopted to carry out a desulfurization test on the wax oil. Wherein, three micromixers all adopt T type structure, and microchannel reactor equivalent diameter is 2mm.
Example 1
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, controlling the residence time of three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor to be 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring the sulfur content to be 0.45% and the desulfurization rate to be 75%.
Example 2
The sulfur content of the wax oil is 1.8 percent, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature of the micro-mixing equipment channel is set to be 50 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of the glacial acetic acid to the sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring the sulfur content to be 0.63 percent and the desulfurization rate to be 65 percent.
Example 3
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 90 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.52 percent and the desulfurization rate of 71 percent.
Example 4
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 400kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.50 percent and the desulfurization rate of 72 percent.
Example 5
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is set to be 600kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.43 percent and the desulfurization rate of 76 percent.
Example 6
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction process is described in reference to example 1, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 2:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 1.41 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring the sulfur content to be 0.63 percent and the desulfurization rate to be 65 percent.
Example 7
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 20:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 14.1 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, controlling the residence time of three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor to be 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring the sulfur content to be 0.396% and the desulfurization rate to be 78%.
Example 8
The sulfur content of the wax oil is 1.8 percent, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 10:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 12.53 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring the sulfur content to be 0.576 percent and the desulfurization rate to be 68 percent.
Example 9
The sulfur content of the wax oil is 1.8 percent, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 20:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 14.1 mu L/min, regulating the flow rate of hydrogen peroxide to be 25.17 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, controlling the residence time of three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor to be 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring the sulfur content to be 0.378 percent and the desulfurization rate to be 79 percent.
Example 10
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 10min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.61% and the desulfurization rate of 66%.
Example 11
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is set to be 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 100min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.38 percent and the desulfurization rate of 79 percent.
Example 12
The sulfur content of the wax oil is 1%, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.41 percent and the desulfurization rate of 77 percent.
Example 13
The sulfur content of the wax oil is 2.87 percent, the diameter of the micro-mixing channel is 0.5mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, controlling the residence time of three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor to be 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring that the sulfur content is 1% and the desulfurization rate is 65%.
Example 14
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 0.1mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.34 percent and the desulfurization rate of 81 percent.
Example 15
The sulfur content of the wax oil is 1.8 percent, the diameter of the micro-mixing channel is 1mm, the length of the micro-mixing channel is 300mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.61% and the desulfurization rate of 66%.
Example 16
The sulfur content of the wax oil is 1.8%, the diameter of the micro-mixing channel is 1mm, the length of the micro-mixing channel is 100mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, and analyzing the sulfur content of the desulfurized wax oil by using a coulomb method to obtain the sulfur content of 0.51 percent and the desulfurization rate of 66 percent.
Example 17
The sulfur content of the wax oil is 1.8 percent, the diameter of the micro-mixing channel is 1mm, the length of the micro-mixing channel is 500mm, the reaction temperature is set to be 80 ℃, the outlet pressure of the micro-channel reactor is 500kpa, and the molar ratio of glacial acetic acid to sulfur is 10:1, the molar ratio of hydrogen peroxide to sulfur is 15:1, regulating the flow rate of wax oil to be 25 mu L/min, regulating the flow rate of glacial acetic acid to be 7.05 mu L/min, regulating the flow rate of hydrogen peroxide to be 18.88 mu L/min, regulating the flow rate of acetonitrile extractant to be 25 mu L/min, keeping the three-phase materials of the wax oil, the catalyst and the oxidant in a microchannel reactor for 20min, analyzing the sulfur content of the desulfurized wax oil by using a coulomb method, and measuring the sulfur content to be 0.45% and the desulfurization rate to be 75%.
By way of example, it can be seen that oxidative extractive desulfurization of wax oil in a microchannel reactor can achieve a desulfurization rate of 65% or more, much higher than 55% reported in the literature, in a shorter residence time. Meanwhile, under the same desulfurization rate, the method needs less oxidant, catalyst and reaction time, and the whole process can be continuously carried out, thereby greatly improving the working efficiency. Although the above examples use acetic acid and hydrogen peroxide as the organic solvent, T-shaped channel structure as the microchannel reactor, and membrane separation as the subsequent step, it will be apparent to those skilled in the art that formic acid, phosphotungstate, peroxyacetic acid as the catalyst, peroxyacetic acid as the oxidant, etc., cross-shaped structures, and other structures are used as the catalyst in the present invention. Improvements and modifications within the spirit of the invention are therefore intended to be covered by the following claims.
Claims (8)
1. A method for oxidizing and extracting wax oil in a microchannel reactor is characterized by comprising the following steps: firstly, mixing wax oil and an oxidation reaction catalyst in a first micro mixer to realize the full contact of the wax oil and the catalyst, then mixing the mixture of the wax oil and the oxidation catalyst and an oxidant in a second micro mixer, and then reacting through a micro-channel reactor for 10-100min; and finally, after the reaction, enabling the material flow to pass through phase separation equipment, fractionating a water phase to obtain a reaction catalyst for recycling, mixing an oil phase and an extracting agent in a third micro mixer, removing most of oxidation products of sulfur-containing components in the wax oil, and then carrying out phase separation to obtain the desulfurized wax oil.
2. The process of claim 1 wherein the microchannel reactor is operated at a reaction temperature of 50 to 90 ℃ and a microchannel reactor outlet pressure of 400 to 600kPa.
3. The method according to claim 1, wherein the molar ratio of oxidant to sulfur is 2:1-20, the molar ratio of catalyst to sulfur is 10-20, the mass ratio of extractant to wax oil is 2:1, and the residence time of the mixture of wax oil, oxidant and catalyst in the microchannel reactor is 10-100 min.
4. The method of claim 1, wherein the catalyst and oxidant are mixed in a first micromixer, the wax oil is mixed with the mixture in a second micromixer, the mixture is preheated to the reaction temperature by a temperature control device, and the oil phase is mixed with the extractant in a third micromixer after the reaction.
5. The method of claim 1, wherein the second micromixer, the phase separation apparatus, the microchannel reactor, and the corresponding conduit are in a temperature control device.
6. The method of claim 1, wherein: the method is suitable for oxidative extraction desulfurization of wax oil, the sulfur content of the wax oil is 1-2.87%, and the desulfurization rate of the method is not lower than 65%.
7. The process according to claim 2, wherein the channels used in the micromixer have an equivalent diameter of 0.1 to 1mm and a length of 100 to 500mm.
8. The process of claim 3 wherein the microchannel reactor has an equivalent diameter of 2mm and a length that is adjustable based on reaction time.
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