CN115491224B - Method for recovering dewaxing solvent in light lubricating oil base oil filtrate - Google Patents
Method for recovering dewaxing solvent in light lubricating oil base oil filtrate Download PDFInfo
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- CN115491224B CN115491224B CN202110670545.3A CN202110670545A CN115491224B CN 115491224 B CN115491224 B CN 115491224B CN 202110670545 A CN202110670545 A CN 202110670545A CN 115491224 B CN115491224 B CN 115491224B
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000002904 solvent Substances 0.000 title claims abstract description 54
- 239000002199 base oil Substances 0.000 title claims abstract description 49
- 239000000706 filtrate Substances 0.000 title claims abstract description 36
- 239000012528 membrane Substances 0.000 claims abstract description 142
- 230000004907 flux Effects 0.000 claims abstract description 62
- 238000001728 nano-filtration Methods 0.000 claims abstract description 40
- 239000003960 organic solvent Substances 0.000 claims abstract description 38
- 239000012466 permeate Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000012530 fluid Substances 0.000 claims abstract description 11
- 230000000149 penetrating effect Effects 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 23
- 239000000314 lubricant Substances 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 5
- 239000010779 crude oil Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 210000001124 body fluid Anatomy 0.000 description 6
- 239000010839 body fluid Substances 0.000 description 6
- 239000002346 layers by function Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000003849 solvent resist ant nanofiltration Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/11—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by dialysis
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1062—Lubricating oils
-
- 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
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
-
- 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
- C10G2400/10—Lubricating 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
- C10G2400/18—Solvents
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the technical field of lubricating oil dewaxing processes, and discloses a method for recycling dewaxing solvent in light lubricating oil base oil filtrate. The method comprises the following steps: (1) Under high pressure condition, contacting the light lubricating oil base oil filtrate with an organic solvent nanofiltration membrane at a low operation circulation flow rate to obtain a permeate; wherein the high pressure is 4.3-10MPa, and the low operation circulation flow is 5-13.5m 3 /h; (2) When the content of the lubricating oil in the penetrating fluid is less than or equal to 2 weight percent, continuing to operate under the condition that the operating pressure is reduced to 2.8-4.2 MPa; (3) And when the permeation flux of the organic solvent nanofiltration membrane is stable, starting successfully, and entering a stable production state. The method can effectively shorten the driving time.
Description
Technical Field
The invention relates to the technical field of lubricating oil dewaxing processes, in particular to a method for recycling dewaxing solvent in light lubricating oil base oil filtrate.
Background
Dewaxing is required in the production of lubricating oils from mineral oils, the earliest and most widely used dewaxing process being solvent dewaxing, which is currently practiced in refineries worldwide. This process can yield both high viscosity lubricant base oils and paraffins, which is also an important reason why other dewaxing processes, such as hydrodewaxing and isodewaxing processes, cannot be completely replaced. However, the solvent dewaxing process is an expensive process requiring solidification of the wax for removal and evaporation of the dewaxing solvent for recovery. The process has very high energy consumption and becomes a bottleneck in the production of lubricating oil. Oil refining technology researchers have been fuelled with new energy-saving technologies for solvent dewaxing units for many years, but the fact that recovery can be accomplished by relying on phase changes of the solvent is not always changed.
Until 1998, exxon used an organic solvent resistant nanofiltration membrane technology in tennessee refinery to recover lube dewaxing solvent (the unit was named) And the method has great breakthroughs in the aspects of energy conservation, emission reduction and yield increase. The research direction is gradually changed to a method of separating by membrane separation without phase change of solvent, but only the report of industrial application of membrane separation to recover lubricating oil dewaxing solvent is +.>Because of->The membrane manufacturer W.R Grace of the device was purchased multiple times later and had no more membrane produced, and was therefore self-containedAfter industrial application reports, no second set of application devices are reported in the world in the aspect of recovering the lubricating oil dewaxing solvent through membrane separation. Researchers have not stopped studying applications in this regard. However, the subsequent studies are limited to laboratory experiments, and no report is made on the industrial test aspect.
In fact, the start-up of an industrial-size OSN membrane lube dewaxing solvent recovery unit is a difficult task, and the ordinary direct start-up method consumes a long time, so that the rejection rate of the membrane is difficult to increase, and the availability of the OSN membrane in recovering lube dewaxing solvent is easily suspected.
Therefore, the method for recovering dewaxing solvent in light lubricating oil base oil filtrate by adopting OSN has important significance.
Disclosure of Invention
The invention aims to overcome the defects that the driving time for separating and recovering the dewaxing solvent of the light lubricating oil by using an industrial grade OSN membrane in the prior art is long and the rejection rate of the membrane is difficult to increase.
In order to achieve the above objects, the present invention provides a method for recovering dewaxing solvent in light lubricant base oil filtrate, wherein the method comprises:
(1) Under high pressure condition, contacting the light lubricating oil base oil filtrate with an organic solvent nanofiltration membrane at a low operation circulation flow rate to obtain a permeate; wherein the high pressure is 4.3-10MPa, and the low operation circulation flow is 5-13.5m 3 /h；
(2) When the content of the lubricating oil in the penetrating fluid is less than or equal to 2 weight percent, continuing to operate under the condition that the operating pressure is reduced to 2.8-4.2 MPa;
(3) And when the permeation flux of the organic solvent nanofiltration membrane is stable, starting successfully, and entering a stable production state.
According to the technical scheme, the dewaxing solvent in the light lubricating oil base oil filtrate is recovered by adopting the industrial-grade asymmetric OSN membrane by adopting the method, and the time for the device to stably run can be shortened by more than 40 percent; moreover, the method is convenient to operate, and no impurity is brought to industrial devices.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for recycling dewaxing solvent in light lubricating oil base oil filtrate, wherein the method comprises the following steps:
(1) Under high pressure condition, contacting the light lubricating oil base oil filtrate with an organic solvent nanofiltration membrane at a low operation circulation flow rate to obtain a permeate; wherein the high pressure is 4.3-10MPa, and the low operation circulation flow is 5-13.5m 3 /h；
(2) When the content of the lubricating oil in the penetrating fluid is less than or equal to 2 weight percent, continuing to operate under the condition that the operating pressure is reduced to 2.8-4.2 MPa;
(3) And when the permeation flux of the organic solvent nanofiltration membrane is stable, starting successfully, and entering a stable production state.
The inventors of the present invention found that: in the industrial test of membrane separation recovery lubricating oil dewaxing solvent, the solvent oil content of the pressure recovery of adopting membrane separation normal operating is always very high, and the trend of reduction can be seen more than ten days of operation, and the system is under high pressure condition through adjusting the frequency of a material conveying pump, meanwhile, the circulating flow is maintained under low operation circulating flow through adjusting the frequency of a circulating pump, and the supporting layer of the membrane is compressed during high pressure operation, so that the stable state can be reached in a short time, and further, enough stable supporting force can be provided for the functional layer of the membrane to enable the functional layer to reach the stable state quickly, so that the driving time can be shortened.
In the invention, it is to be noted that: the phrase "the content of lubricating oil in the permeate is less than or equal to 2 wt.%" means that: the penetrating fluid contains lubricating oil, and the content of the lubricating oil is less than or equal to 2 weight percent based on the total weight of the penetrating fluid.
According to the present invention, even in the case of the high pressure and low operation cycle flow rate defined above, the start-up time can be shortened, but in the present invention, it is preferable that the conditions of the high pressure include: 4.4-8MPa, wherein the conditions of low operation circulation flow comprise: 7-13m 3 /h; more preferably, the high pressure condition includes: 4.5-6MPa, wherein the conditions of low operation circulation flow comprise: 8-12m 3 And/h. In the present invention, the driving time can be further shortened under the preferable condition.
According to the invention, in step (1), the permeation flux of the stabilized organic solvent nanofiltration membrane is 200-550L/branch/h, preferably 300-520L/branch/h.
According to the invention, in step (1), the conditions of the contacting include: the temperature is 10 to 50 ℃, preferably 20 to 40 ℃, more preferably 25 to 35 ℃.
According to the invention, in step (2), when the content of lubricating oil in the permeate is 0.1-2 wt%, continuing to operate under the condition that the operating pressure is 3-4 MPa; in the present invention, the content of the lubricating oil in the permeate and the operating pressure are limited to the aforementioned ranges, meaning that the operation is stable.
According to the invention, the method further comprises: during the operation of the method, the low operating cycle flow is fixed. In the invention, the low operation circulation flow is kept unchanged, the principle is that the supporting layer of the membrane reaches a stable compression state as soon as possible by adjusting the high pressure condition, the functional layer of the membrane is provided with stable support, and the functional layer reaches a stable state as soon as possible.
According to the invention, the content of lubricating oil in the permeate liquid and the permeation flux of the organic solvent nanofiltration membrane are in gradient change.
According to the present invention, in step (3), the conditions for stabilizing the permeation flux of the organic solvent nanofiltration membrane include: the flux of the nanofiltration membrane was reduced by less than 1% in 24 hours. That is, in the present invention, the decrease in permeation flux of the organic solvent nanofiltration membrane by less than 1% in 24 hours is used as a criterion for the running flux stabilization of the membrane.
According to the present invention, it is preferable that in step (3), two conditions, that is, the content of the lubricating oil in the permeate and the permeation flux of the organic solvent nanofiltration membrane are simultaneously defined, are simultaneously satisfied, which means that the start-up is successful and a stable production state can be entered. Preferably, the conditions of successful driving include: the permeation flux of the organic solvent nanofiltration membrane is 300-520L/branch/h, and the content of lubricating oil in the permeate liquid is 0.1% -2%; more preferably, the conditions for successful driving include: the permeation flux of the organic solvent nanofiltration membrane is 530-580L/branch/h, and the content of lubricating oil in the permeation liquid is 1.3-1.5%.
According to the present invention, in step (3), the conditions of the stable production state include: the content of lubricating oil in the permeate liquid is 0.3-1.8 wt%, and the permeation flux of the organic solvent nanofiltration membrane is 220-550L/branch/h; preferably, the content of lubricating oil in the permeate is 1-1.3 wt%, and the permeation flux of the organic solvent nanofiltration membrane is 460-510L/branch/h.
According to the invention, the organic solvent nanofiltration membrane (OSN) is one or more selected from a hollow fiber membrane module, a roll membrane module, a tubular membrane module and a plate membrane module, preferably a roll membrane module, and in the invention, the OSN membrane is of an asymmetric structure, is made of a glassy polymer, preferably a polyimide polymer, and most preferably is a P84 polyimide asymmetric nanofiltration membrane.
According to the invention, the molecular weight cut-off of the nanofiltration membrane of the organic solvent is 280-400Da, preferably 300-380Da; preferably, the membrane area of the organic solvent nanofiltration membrane is 20-40m 2 A/B/A membrane, preferably 20-30m 2 And/or a support.
According to the invention, the length of the membrane module of the organic solvent nanofiltration membrane is 0.8-1.2m, preferably 0.9-1.1m, and the diameter of the membrane module is 6-10 inches, preferably 7-9 inches. In the invention, the organic solvent nanofiltration membrane is purchased from Yingchang specialty Chemie under the brand PM280, and the membrane component is a coiled membrane with the length of 1m and the diameter of 8 inches.
According to the invention, the light lubricant base oil filtrate contains a light lubricant base oil and a dewaxing solvent.
According to the invention, the light lubricant base oil is present in an amount of from 20 to 26 wt.% and the dewaxing solvent is present in an amount of from 74 to 80 wt.%, based on the total weight of the light lubricant base oil filtrate; preferably, the light lubricant base oil is present in an amount of 21 to 25 wt.% and the dewaxing solvent is present in an amount of 75 to 79 wt.%, based on the total weight of the light lubricant base oil filtrate.
According to the invention, the light lubricant base oil is a crude oil fraction having a boiling range of 280-500 ℃; preferably, the light lubricating oil base oil is selected from one or more of the group consisting of normal four-wire, two-wire and three-wire cut obtained by distillation of crude oil, most preferably a three-wire cut lubricating oil base oil feedstock.
In the invention, the light lubricating oil raw oil is from a China petrochemical metallocene company refinery, wherein the light lubricating oil raw oil comprises the following components in percentage by weight: the light lubricant base oil content was 24% and the dewaxing solvent content was 76%.
According to the invention, the dewaxing solvent is an aromatic hydrocarbon and C 3 -C 8 Is a mixture of monoketones of (2).
According to the present invention, preferably, the aromatic hydrocarbon is monoalkylbenzene and/or benzene, more preferably, the alkyl group in the monoalkylbenzene is C 1 -C 4 Further preferably, the aromatic hydrocarbon is selected from one or more of toluene, ethylbenzene and propylbenzene.
According to the present invention, preferably, the monoketone is selected from one or more of methyl ethyl ketone, acetone, 2-butanone, 2-pentanone, 3-pentanone and 2-hexanone.
According to the present invention, preferably, the dewaxing solvent is a mixture of methyl ethyl ketone and toluene.
According to the present invention, preferably, the weight ratio of the monoketone to the aromatic hydrocarbon is (50:50) - (75:25), more preferably (50:50) - (70:30).
According to the invention, the method further comprises: before step (1), the organic solvent nanofiltration membrane is washed. Specifically, in the invention, firstly, dewaxing solvent is added into a membrane separation device for membrane washing, after the membrane washing is finished, dewaxing solvent in an evacuation device is added into light base oil dewaxing filtrate for operation until flux stability and retention rate reach target requirements, and finally, the operation pressure of the system is regulated to a preset pressure, and the circulation flow of the system is unchanged.
According to the invention, the cleaning conditions include: the film washing time is 0.1-24h, preferably 0.5-8h, more preferably 1-3h; the film washing pressure is 0-5MPa, preferably 0.2-2MPa, more preferably 0.5-1MPa; the circulating flow rate of the film washing solvent is 1-20m 3 Preferably 5-18m 3 Preferably from 8 to 15m 3 /h。
According to the invention, the permeation flux of the OSN membrane can reach a steady state when the system is operated at high pressure for 3 to 10 days, preferably 4 to 8 days, and at the same time the content of lubricating oil in the permeate can be less than 2 wt.%.
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the content parameter of the lubricating oil is measured by a thermogravimetric method; the flux of the membrane is directly read by the device with its own flowmeter.
Example 1
This example illustrates a process for recovering dewaxing solvent from a light lubricant base oil filtrate using the process of the present invention.
Light lubricant base oil filtrate: a three-wire base oil filtrate from a lube light ketone production unit, the three-wire base oil filtrate having a three-wire base oil concentration of 24%.
Organic solvent nanofiltration membrane: the industrial-grade size OSN film is adopted for starting, the OSN film is selected from 8-inch film components of Yingzhang special chemical PM280 film, the film components are roll-type film components, the diameter of the film components is 8 inches, and the length of the film components is 1m; OSN film having a film area of 24m 2 And/membrane, the molecular weight cut-off is 280Da.
(1) The temperature is maintained at 30 ℃ in the whole driving experiment process, firstly, dewaxing solvent (the dewaxing solvent is mixed solvent of butanone and toluene, wherein the mass ratio of the butanone to the toluene is 3:2) is added into a membrane separation pilot test device system, a material conveying pump is started to control the pressure to be 0.5MPa, a circulating pump is started after 2min, and the circulating flow is controlled to be 15m 3 And (h) performing a membrane washing test, and evacuating after membrane washing for 3hA film washing solvent in the system;
(2) Gradually adding the three-wire base oil filtrate into the device system, then adjusting the frequency of a material conveying pump to increase the pressure in the system to 4.5MPa, and adjusting the frequency of a circulating pump to maintain the circulating flow at 12m 3 And/h, obtaining a penetrating fluid;
at this time, the permeation flux of the OSN film is 1200L/branch/h, and the content of the test lubricating oil of the permeate is 8.2%;
after 2 days of operation, the permeation flux of the OSN film is reduced to 600L/branch/h, and the content of the test lubricating oil of the permeate is 7.3 percent;
after 3 days of operation, the permeation flux of the OSN film is reduced to 540L/branch/h, and the content of the test lubricating oil of the permeate is 5.8%;
after 4 days of operation, the permeation flux of the OSN film is maintained at 530-540L/branch/h, and the content of the test lubricating oil of the permeate is 2.2%;
after 5 days of operation, the permeation flux of the OSN film is maintained at 530-540L/branch/h, the content of the test lubricating oil of the permeate is 1.4%, and the operation is successful;
the operation pressure is reduced to 3.5MPa for operation;
after 1 day of operation, the permeation flux of the OSN film is stabilized at 480-490L/branch/h, the content of lubricating oil in the permeation liquid is 1.3%, and the OSN film enters a stable production state.
Example 2
This example illustrates a process for recovering dewaxing solvent from a light lubricant base oil filtrate using the process of the present invention.
The light lube base oil filtrate and organic solvent nanofiltration membrane were the same as in example 1.
(1) The temperature is maintained at 35 ℃ in the whole driving experiment process, firstly dewaxing solvent which is the same as that in the embodiment 1 is added into a device system, the control pressure of a material conveying pump is started to be 0.8MPa, a circulating pump is started after 2min, and the circulating flow is controlled to be 12m 3 Carrying out a film washing test, and evacuating a film washing solvent in the system after film washing for 2 hours;
(2) Gradually adding the same three-wire reducing base oil filtrate as in example 1 into the device system, and then adjusting the frequencies of the feed pump and the circulating pump to maintain the system pressure at 5MPa and the system circulating flow dimensionHeld at 10m 3 And/h, obtaining a penetrating fluid;
at the moment, the permeation flux of the OSN film is 1400L/branch/h, and the content of lubricating oil in the permeation liquid is 8.2%;
continuously maintaining the pressure and the circulation flow to operate the device, gradually and slowly reducing the permeation flux of the membrane along with the increase of the operation time, reducing the permeation flux of the OSN membrane to 620L/branch/h after 2 days of operation, and taking the permeation liquid to test the content of lubricating oil to be 7.2%;
after 3 days of operation, the permeation flux of the OSN film is reduced to 580L/branch/h, and the content of the test lubricating oil of the permeate is 3.2 percent;
after 4 days of operation, the permeation flux of the OSN film is reduced to 570-580L/branch/h, the content of the test lubricating oil of the permeate is 1.5%, and the operation is successful;
the operating pressure is reduced to 3.5MPa for operation, the flux of the OSN film is stabilized at 500-510L/branch/h after one day, the lubricating oil content in the penetrating fluid is 1.3 percent, and the stable production state is achieved.
Example 3
This example illustrates a process for recovering dewaxing solvent from a light lubricant base oil filtrate using the process of the present invention.
The light lube base oil filtrate and organic solvent nanofiltration membrane were the same as in example 1.
(1) The temperature was maintained at 25℃throughout the start-up experiment, first, the same dewaxing solvent as in example 1 was added to the system, the feed pump was turned on to control the pressure at 1MPa, the circulation pump was turned on after 2min, and the circulation flow rate was controlled at 8m 3 Carrying out a film washing test, and evacuating a film washing solvent in the system after film washing for 1 h;
(2) Gradually adding the same three-wire reducing base oil filtrate as in example 1 into the device system, then adjusting the frequencies of the feed pump and the circulating pump to maintain the system pressure at 6MPa and the system circulating flow to continuously maintain 8m 3 And/h, obtaining a penetrating fluid;
at the moment, the permeation flux of the OSN film is 1380L/branch/h, and the content of lubricating oil in the permeation liquid is 8.0%;
continuously maintaining the pressure and the circulation flow to operate the device, gradually and slowly reducing the permeation flux of the membrane along with the increase of the operation time, reducing the permeation flux of the OSN membrane to 600L/branch/h after 2 days of operation, and taking the permeation liquid to test the content of lubricating oil to be 7.0%;
after 3 days of operation, the permeation flux of the OSN film is reduced to 570L/branch/h, and the content of the test lubricating oil of the permeate is 3.0 percent;
after 4 days of operation, the permeation flux of the OSN film is reduced to 560-570L/branch/h, the content of the test lubricating oil of the permeate is 1.3 percent, and the operation is successful;
the operating pressure is reduced to 3.5MPa, the flux of the OSN film is stabilized at 460-470L/branch/h after one day, the lubricating oil content in the penetrating fluid is 1.3%, and the stable production state is achieved.
Comparative example 1
The OSN membrane and membrane separation unit used and the light lube base oil filtrate and experimental temperature were exactly the same as in example 1. First dewaxing solvent is added to the system in preparation for membrane wash. The method of washing the film was the same as in example 1. The material conveying pump is started to control the pressure to be 0.5MPa, the circulating pump is started after 2min, and the circulating flow is controlled to be 15m 3 And (3) carrying out a membrane washing test, evacuating a membrane washing solvent in the system after membrane washing for 3 hours, adding light lubricating oil base oil filtrate into a membrane separation device, regulating the frequencies of a material conveying pump and a circulating pump to keep the system pressure at about 3.5MPa, and keeping the circulating flow at 12m 3 And/h, wherein the permeation flux of the membrane is 1000L/branch/h, and the content of the tested lubricating oil of the permeate body fluid is 8.2%.
Continuing to operate the device, the permeation flux of the membrane is continuously reduced along with the increase of the operation time, and when the device is operated for 3 days, the permeation flux of the membrane is 650L/branch/h, and the content of the test lubricating oil of the permeate body fluid is 8.0%;
when the device is operated for 6 days, the permeation flux of the membrane is reduced to 530L/branch/h, and the content of lubricating oil in the permeation liquid is 7.2%;
when the device is operated for 9 days, the permeation flux of the membrane is reduced to 500L/branch/h, and the content of lubricating oil in the permeation liquid is 6.0%;
the permeation flux of the membrane is stabilized at 480-490L/branch/h when the device is operated for 12 days, and the lubricating oil content in the permeation liquid is 3.1 percent;
when the device runs for 13 days, the permeation flux of the membrane is stabilized at 480-490L/branch/h, the content of lubricating oil in the permeation liquid is 1.3%, and the device is successfully started and enters a stable production state.
Comparative example 2
The OSN membrane and membrane separation unit used and the light lube base oil filtrate and experimental temperature were exactly the same as in example 2. First dewaxing solvent is added to the system in preparation for membrane wash. The method of washing the film was the same as in example 2. The material conveying pump is started to control the pressure to be 0.8MPa, the circulating pump is started after 2min, and the circulating flow is controlled to be 12m 3 And (h) performing a membrane washing test, evacuating a membrane washing solvent in the system after membrane washing for 2h, adding light lubricating oil base oil filtrate into a membrane separation device, adjusting the frequencies of a material conveying pump and a circulating pump to keep the system pressure at about 3.5MPa, and keeping the circulating flow at 10m 3 And/h, wherein the permeation flux of the membrane is 1100L/branch/h, and the content of the tested lubricating oil of the permeate body fluid is 8.3%. Continuing to operate the device, the permeation flux of the membrane is continuously reduced along with the increase of the operation time, and when the device is operated for 3 days, the permeation flux of the membrane is 660L/branch/h, and the content of the test lubricating oil of the permeate body fluid is 8.0%; when the device is operated for 6 days, the permeation flux of the membrane is reduced to 550L/branch/h, and the content of lubricating oil in the permeation liquid is 7.4 percent; when the device is operated for 9 days, the permeation flux of the membrane is reduced to 530L/branch/h, and the content of lubricating oil in the permeation liquid is 5.9%; the permeation flux of the membrane is stabilized at 500-510L/branch/h when the device is operated for 12 days, and the lubricating oil content in the permeation liquid is 3.0%; when the device runs for 13 days, the permeation flux of the membrane is stabilized at 500-510L/branch/h, the content of lubricating oil in the permeation liquid is 1.4%, and the device is successfully started and enters a stable production state.
Comparative example 3
The OSN membrane and membrane separation unit used and the light lube base oil filtrate and experimental temperature were exactly the same as in example 2. First dewaxing solvent is added to the system in preparation for membrane wash. The method of washing the film was the same as in example 3. The material conveying pump is started to control the pressure to be 0.1MPa, the circulating pump is started after 2min, and the circulating flow is controlled to be 8m 3 And (h) performing a membrane washing test, evacuating a membrane washing solvent in the system after membrane washing for 1h, adding light lubricating oil base oil filtrate into a membrane separation device, and adjusting the frequency of a feed pump to enable the system to be usedThe pressure is kept at about 3.5MPa, and the circulating flow is kept at 8m 3 And/h, wherein the permeation flux of the membrane is 890L/branch/h, and the content of the tested lubricating oil of the permeate body fluid is 8.1%. Continuing to operate the device, the permeation flux of the membrane is continuously reduced along with the increase of the operation time, and when the device is operated for 3 days, the permeation flux of the membrane is 540L/branch/h, and the content of the test lubricating oil of the permeate body fluid is 7.8%; when the device is operated for 6 days, the permeation flux of the membrane is reduced to 510L/branch/h, and the content of lubricating oil in the permeation liquid is 6.4 percent; when the device is operated for 9 days, the permeation flux of the membrane is reduced to 490L/branch/h, and the content of lubricating oil in the permeation liquid is 4.9%; the permeation flux of the membrane is stabilized at 460-470L/branch/h when the device is operated for 12 days, and the lubricating oil content in the permeation liquid is 2.8%; when the device runs for 13 days, the permeation flux of the membrane is stabilized at 460-470L/branch/h, the content of lubricating oil in the permeation liquid is 1.3%, and the device is successfully started and enters a stable production state.
The results show that according to the embodiments 1-3 of the method provided by the invention, the solvent of the membrane separation system is used for preprocessing the membrane, so that the molecules of the functional layer material of the membrane can be stretched to the greatest extent, the membrane can adapt to the separation environment quickly, the interception effect of the membrane can be exerted in a shorter time, and the operating pressure is higher, and the supporting layer of the membrane provides a larger reaction force, so that the functional layer is sufficiently stably supported, the stability is good, the driving time can be shortened, and the obvious better effect is achieved.
Comparative example 1, comparative example 2 and comparative example 3 do not employ the technical scheme of the present invention, and the pressure is low, resulting in a long driving time.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (16)
1. A process for recovering dewaxing solvent from a light lubricant base oil filtrate, said process comprising:
(1) Under high pressure condition, contacting the light lubricating oil base oil filtrate with an organic solvent nanofiltration membrane at a low operation circulation flow rate to obtain a permeate; wherein the high pressure is 4.3-10MPa, and the low operation circulation flow is 5-13.5m 3 /h；
(2) When the content of the lubricating oil in the penetrating fluid is less than or equal to 2 weight percent, continuing to operate under the condition that the operating pressure is reduced to 2.8-4.2 MPa;
(3) When the permeation flux of the organic solvent nanofiltration membrane is stable, the starting is successful, and the organic solvent nanofiltration membrane enters a stable production state;
wherein, in the step (3), the condition that the permeation flux of the organic solvent nanofiltration membrane is stable includes: the flux of the nanofiltration membrane is reduced by less than 1% in 24 hours;
wherein in step (3), the conditions for successful driving include: the permeation flux of the organic solvent nanofiltration membrane is 300-520L/branch/h, and the content of lubricating oil in the permeation liquid is 0.1-2 wt%;
wherein in step (3), the conditions for stabilizing the production state include: the content of lubricating oil in the permeate liquid is 0.3-1.8 wt%, and the permeation flux of the organic solvent nanofiltration membrane is 220-550L/branch/h.
2. The method of claim 1, wherein the high pressure is 4.4-8MPa and the low run recycle flow is 7-13m 3 /h。
3. The method of claim 1, wherein the high pressure is 4.5-6MPa and the low run recycle flow is 8-12m 3 /h。
4. The method according to claim 1, wherein in step (1), the permeation flux after the organic solvent nanofiltration membrane is stabilized is 200-550L/branch/h;
and/or in the step (2), when the content of the lubricating oil in the permeate is 0.1-2 wt%, continuing to operate under the condition that the operating pressure is 3-4 MPa.
5. The method of any one of claims 1-4, wherein the method further comprises: during the operation of the method, the low operating cycle flow is fixed.
6. The method of claim 1, wherein in step (1), the contacting conditions comprise: the temperature is 10-50 ℃.
7. The method of claim 1, wherein in step (1), the contacting conditions comprise: the temperature is 20-40 ℃.
8. The method of claim 1, wherein in step (1), the contacting conditions comprise: the temperature is 25-35 ℃.
9. The method of claim 1, wherein the organic solvent nanofiltration membrane has a molecular weight cut-off of 280-400Da;
and/or the membrane area of the organic solvent nanofiltration membrane is 20-40m 2 A support membrane;
and/or the length of the membrane component of the organic solvent nanofiltration membrane is 0.8-1.2m, and the diameter of the membrane component is 6-10 inches.
10. The method of claim 9, wherein the organic solvent nanofiltration membrane has a molecular weight cut-off of 300-380Da.
11. The method of claim 1, wherein the light lubricant base oil filtrate contains a light lubricant base oil and a dewaxing solvent;
and/or, the light lubricant base oil is present in an amount of from 20 to 26 wt% and the dewaxing solvent is present in an amount of from 74 to 80 wt%, based on the total weight of the light lubricant base oil filtrate;
and/or, the light lubricant base oil is a crude oil fraction having a boiling range of 280-500 ℃;
and/or the light lubricating oil base oil is selected from one or more of a normal four-wire, a two-wire and a three-wire reducing oil obtained by crude oil distillation.
12. The method of claim 11, wherein the dewaxing solvent is an aromatic hydrocarbon and C 3 -C 8 Is a mixture of monoketones of (2).
13. The method of any one of claims 1-4, 6-12, wherein the method further comprises: before step (1), the organic solvent nanofiltration membrane is washed.
14. The method of claim 5, wherein the method further comprises: before step (1), the organic solvent nanofiltration membrane is washed.
15. The method of claim 13, wherein the cleaning conditions comprise: the membrane washing time is 0.1-24h, the membrane washing pressure is 0.2-5MPa, and the circulating flow of the membrane washing solvent is 1-20m 3 /h。
16. The method of claim 14, wherein the cleaning conditions comprise: the membrane washing time is 0.1-24h, the membrane washing pressure is 0.2-5MPa, and the circulating flow of the membrane washing solvent is 1-20m 3 /h。
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