CN1886657A - Application of test for residual wax contamination in basestocks to correlate with the low temperature viscometric properties of fully formulated oils - Google Patents
Application of test for residual wax contamination in basestocks to correlate with the low temperature viscometric properties of fully formulated oils Download PDFInfo
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Abstract
Rapid determination of low temperature residual wax contamination in basestock oil provides a bases for real time correlation of basestock quality with the low temperature viscometric properties of fully formulated oils made using said basestock oil.
Description
Technical field
The present invention relates to be used to predict the method for the low temperature viscosity (viscometricproperty) of full formulated oil, this method is based on to being used for producing the analysis of these oily raw material wax contents.
Correlation technique
At the dewaxing technique that is used for producing crude lube stock, fault in the technology or poor efficiency can cause existing in the raw material wax, and the amount of wax has surpassed normal raw material and produced the acceptable limit.This wax contamination or excessive wax may since underlying cause produce: the crack of the wax filter cloth by being used for solvent dewaxing process or the wax that tear leaks; Or the overload of solvent dewaxing process; Or the raw material branch road of the catalytic bed by being used for WITH CATALYTIC DEWAXING TECHNIQUE; Or the overload by WITH CATALYTIC DEWAXING TECHNIQUE; Or because catalyst activity or poor selectivity; Or because the thick oil of technology or charging and expection significantly different cause the dewaxing condition inappropriate.
When dewaxing technique is not mistake or poor efficiency, existing wax is considered to " acceptable " in the oil herein, and by comparison, residual wax contamination can cause by any formulated oil of this feedstock oil preparation that contains remaining wax defective at low temperatures, that is, has unsatisfied low temperature viscosity.
But the existence of this residual wax contamination may not be passed through standard wax detection technique such as pour point or cloud point and detect easily definite or detection.That is to say, contain the raw material of the remaining wax of q.s, can cause using any formulated oil of this feedstock production not have satisfied low temperature viscosity, but when checking with standard pour point and/or cloud point detection technique, it still may be shown as up to specification.
Residual wax contamination is if sufficiently high words may cause wax crystal growth in raw material.Wax crystal can cause the height non newtonian of low temperature viscosity to increase in full formulated oil, causes at low temperatures high viscosity and/or poor pumpability.Wax crystal also can cause filterability reduction or forfeiture in by the full formulated oil of finished product of this feedstock production.In low temperature viscosity or filterability were crucial oil, for example in machine oil or hydraulic oil or the transmission fluid, the reducing or lose of the increase of low temperature viscosity or filterability can cause oily work undesired.Another potential problems of residual wax contamination are, when leaving standstill, wax crystal can form blushing in oil, and this is disadvantageous from client's angle.
Usually the growth of residual wax contamination wax crystal is a process slowly, and has only that just naked eyes are as seen through these crystal in a few days or after a few week.Therefore, use this full formulated oil that contains the crude production of undiscovered residual wax contamination to cause entire block not reach the viscosity requirement.
Most of wax crystals determine that technology depends on the variation substantially of visual inspection or raw material viscosity.Therefore, depend on the example such as the cloud point of macroscopic test, the cloud point of spending the night, and wax blushing outward appearance.The example that depends on the technology that changes substantially of material viscosity is the pour point method, no matter used be original manual pour point method, it can not incline to from the beaker of upset based on crude oil; Or automated process, as the ISL pour point, Phase Technology pour point; Or Herzog rotation pour point method.All these methods all are the wax content acceptable rough wax authentication methods whether that is used for estimating crude oil.They can not be well or are suitable for fully identifying, quantize or the demonstration residual wax contamination.These tests of great majority also are subjective, therefore cause their unreliability and wide precision.
The electrical energy consumption analysis instrument replaces, and its variation by transmitted light or catoptrical intensity or degree change measures that blushing begins and blushing degree or wax crystal form, and has got rid of human factor thereby form from wax crystal detecting.This instrument be can obtain now and cloud point, congealing point and pour point are used for determining.This analyser uses by the light scattering of small sample pond (about 0.15ml) and detects the existence of the solid wax particle that light reflects from it.By optical inductor continuous detecting reflected light.Perhaps, cause transmitted light decay by sample cell by the interference wax crystal, this also is a kind of method that detects the existence of wax.But as mentioned above, for residual wax contamination, cloud point, the cloud point of spending the night and pour point are not enough sensitivities, can not be as the benchmark of the final low temperature viscosity of predicting formulated oil.Sometimes, though full formulated oil has satisfied the regulation of oil about cloud point and/or pour point, but find that but it does not satisfy the low temperature viscosity of the key of oil, for example (CCS) viscosity or miniature rotational viscosimeter (MRV) of cold cranking simulator (coldcranking simulator).
Interrelated in real time between the low temperature viscosity of the residual wax contamination of crude oil and product oil will make it possible to prepare the formulated oil that the low temperature viscosity that satisfies final products requires.
Description of drawings
Fig. 1 shown, determines by prior art, and the MRV result of 20W50 machine oil potpourri is with respect to the function curve of the cloud point of the corresponding Bright Stock crude oil that is used to prepare potpourri.
Fig. 2 shown, determines according to one embodiment of the invention, and the MRV result of 20W50 machine oil potpourri is with respect to the function curve of delta intensity (DI) value of the corresponding Bright Stock crude oil that is used to prepare potpourri.
Fig. 3 has shown in temperature and has reduced to from 14 ℃-2 ℃ of processes, for the relation curve of the delta intensity relative temperature of 4 kinds of Bright Stock crude oil samples, shown approximately+9 ℃ to good related with the low temperature MRV of the 20W50 machine oil of these crude oil mixing of the delta intensity of+5 ℃ of mensuration.
Fig. 4 a, b and c have shown respectively for 13 Bright Stock crude oil samples that are used to prepare 20W50 machine oil potpourri, at the relation curve of 10 ℃, the 6 ℃ relative DI data of the MRV with-2 ℃, shown in the DI of 6 ℃ of mensuration data to be associated most with the low temperature MRV viscosity of being concerned about.
Fig. 5 has shown for the 3 kinds of 600SUS crude oil being surveyed that are used to allocate 20W50 machine oil (prescription 1), the relation curve of DI relative temperature, shown when temperature when 0 ℃ is reduced to-8 ℃, the DI of each sample.
Fig. 6 has shown for the 3 kinds of 600SUS feedstock oils being surveyed that are used to allocate 20W50 machine oil (prescription 2), the relation curve of DI relative temperature, shown when temperature when 0 ℃ is reduced to-8 ℃, the DI of each sample.
Fig. 7 shown for be used to be allocated as machine oil survey the neutral light feedstock oils of two kinds of Group II, the relation curve of DI relative temperature, shown when temperature when-15 ℃ are reduced to-21 ℃, the DI of each sample.
Summary of the invention
The present invention relates to a kind of method, this method is used for determining in real time whether feedstock oil is suitable for use as the raw material of producing the full formulated oil that satisfies the requirement of product low temperature viscosity, and in the first embodiment, this method comprises:
(a) at least one low temperature viscosity of the full formulated oil of selection;
(b) produce training set (training set) through the following steps:
(1) sample of the suitable candidate's of acquisition dewaxing feedstock oil is to be used to produce full formulated oil;
(2) the feedstock oil sample is heated sufficiently long time and be heated to sufficiently high temperature,, preferably, remove all water that exists in the sample simultaneously so that the wax in the sample all melts;
(3) sample of stirring through heating is to guarantee homogeneity;
(4) in sample cell (sample cell), oil is cooled to and is being higher than 20 ℃ of crude oil regulation pour points and is being lower than temperature between 5 ℃ of the crude oil regulation pour points, this sample cell is equipped with the heating and cooling device, and is provided for measuring reflection of light or the optical transmission that produces from the source;
(4a) depend on the stability of instrument after the scale of signal and the temperature variation, wait for that sample and test pool settle out;
(5) stationary phase is later at the temperature survey scattering/reflected light of step 4 or pass the signal of the transmitted light of sample, to obtain the first intensity reading;
(6) make sample keep 1 minute to 3 hours (preferred about 30 minutes to 90 minutes) in the temperature of step 4;
(7) signal of measuring scattering/reflected light or transmitted light when retention time of step 6 finishes to be obtaining the second intensity reading, and measures any variation (signal delta intensity) of the signal intensity between the first signal reading and secondary signal reading;
(8) use feedstock oil formulated oil product, and selected low temperature viscosity in the mensuration step (a) relevant with product quality;
(9) as required, use to be higher than 20 ℃ of regulation pour points and the different temperatures repeating step 1-8 that is lower than between 5 ℃ of the regulation pour points, until the relation of observing signal delta intensity and selected formulated oil viscosity under the temperature of step (4) and (6);
(10) make in the signal delta intensity and the selected low temperature viscosity of the temperature of step (4) and (6) interrelated;
(c) make crude oil experience step 1-8;
(d) signal delta intensity and the Relational database with crude oil in the step (c) compares, and whether available described crude oil prepares the formulated oil with selected low temperature viscosity with prediction.
Not necessarily and preferably, can carry out step 9a, wherein make one or more extra samples of identical or different dewaxing feedstock oil experience step 1-9 respectively, to obtain for multiple crude oil sample the database of the mutual relationship of signal delta intensity and selected formulated oil low temperature viscosity.
In second embodiment, the present invention relates to a kind of method, this method is used for determining in real time whether feedstock oil is suitable for use as the raw material of producing the full formulated oil that satisfies the requirement of product low temperature viscosity, and this method comprises:
(a) at least one low temperature viscosity of the full formulated oil of selection;
(b) produce training set through the following steps:
(1) sample of the suitable candidate's of acquisition dewaxing feedstock oil is to be used to produce full formulated oil;
(2) the feedstock oil sample is heated sufficiently long time and be heated to sufficiently high temperature,, and remove all water that exists in the sample so that the wax in the sample all melts;
(3) sample of stirring through heating is to guarantee homogeneity;
(4) put about 20 ℃ and put about 5 ℃ from being higher than the fuel oil meter constant inclination to being lower than the fuel oil meter constant inclination, preferably put about 10 ℃ and put about 2 ℃ to being lower than the fuel oil meter constant inclination from being higher than the fuel oil meter constant inclination, in sample cell, sample is slowly cooled off, this sample cell is equipped with the heating and cooling device, and is provided for measuring reflection of light or the optical transmission that produces from the source; Measure reflect/scatter or transmission signal, and the ongoing variation of measure signal intensity (signal delta intensity);
(5) oil that feedstock oil is produced is used in allotment, and selected low temperature viscosity in the measurement step (a) relevant with product quality;
(5a) not necessarily, for one or more additional samples repeating steps 1-5 of identical or different dewaxing feedstock oil, to obtain database for the selected relatively low temperature viscosity of signal delta intensity of multiple crude oil sample;
(6) make signal delta intensity and selected low temperature viscosity interrelated;
(c) make crude oil experience step 1-4;
(d) signal delta intensity and the Relational database with crude oil in the step (c) compares, and whether available described crude oil prepares the formulated oil with selected low temperature viscosity with prediction.
Not necessarily, for all unknown samples in the step (c), concerning of signal delta intensity and selected low temperature viscosity information itself can be included in the database, as step (e).
In the step 4 and 6 of embodiment 1, or in the step 4 of embodiment 2, can change in the step 6 of the temperature of each step and embodiment 1 or the duration in the step 4 of embodiment 2, to obtain being fit to effective mutual relationship.Can be as quickening this process by temperature ramp (temperature ramp) in the step 4 of enforcement scheme 2 to limited sample use embodiment 2, to select suitable target temperature to be used for the step 4 of embodiment 1, or select suitable temperature ramp, thereby obtain comprehensive database and mutual relationship.
The low temperature viscosity of full formulated oil includes, but is not limited to miniature rotational viscosimeter (MRV) viscosity and yield stress, cloth network gram Field viscosity, scans cloth network gram Field viscosity, cold start simulation (CCS) and pour point.
By professional oneself decision, for his concrete feedstock oil, formulated oil finished product and selected low temperature viscosity, what constitutes the available mutual relationship of selected low temperature viscosity and DI.But, generally speaking, the temperature when selected low temperature viscosity and signal intensity begin to increase, the temperature when just signal intensity begins to change, promptly the initial temperature of DI (onset temperature) is interrelated.When adopting temperature ramp, determined this mutual relationship.As an alternative and same available, the temperature of selected low temperature viscosity when reaching given signal delta intensity is interrelated.Have, selected low temperature viscosity is with interrelated in the delta intensity to the signal of measuring under the fixed temperature again.Given signal delta intensity, given temperature or DI initial temperature determined by the generation of training set, and in case be allocated as the allotment finished product, qualified corresponding with selected low temperature viscosity by oil.Therefore, signal delta intensity, the relation between fixed temperature or DI initial temperature and the selected low temperature viscosity of giving have been determined DI maximal value under specified temp crude oil, the temperature the when temperature under specific DI value or DI initially take place, be higher than this value, then the formulated oil product that is made by crude oil can not satisfy the low temperature viscosity of preliminary election.
Therefore, this mutual relationship makes the acceptance or rejection of the initial preliminary election low temperature viscosity with the formulated oil products that prepare with different oil of DI or DI be correlated with.In temperature ramp, under specified temp, each oil of surveying (and all are used for the crude oil of commercial formulated oil subsequently) that produces training set will produce specific DI, or demonstration DI's is initial.
In embodiment 1, the professional has estimated the acceptance or rejection for the selected low temperature viscosity of specific formulated product, and the temperature when having determined to compare the DI of underproof crude oil and observe this situation with the DI of qualified crude oil for underproof oil.This temperature promptly becomes for all unknown crude oil of considering to be used to produce specific formulated oil product and carries out the temperature that DI measures.
In embodiment 2, the professional has also estimated the acceptance or rejection for the selected low temperature viscosity of specific formulated product, and determined oily temperature when defective in temperature ramp, under this temperature, observe the initial change (DI initial temperature) of signal intensity, or produce the specific DI of the crude oil of substandard product.This temperature promptly becomes in temperature ramp for the unknown oil of considering to be used to produce specific formulated oil product to be observed the initial of delta intensity or reaches the temperature of specific DI, and its explanation crude oil is not suitable for allotment.
In enforcement of the present invention, sample is heated the sufficiently long time and is heated to sufficiently high temperature, so that the wax in the sample all melts, remove all water that exists in the sample simultaneously; Described temperature is generally about 50 ℃-150 ℃, and preferred about 60 ℃-120 ℃, more preferably from about 100 ℃; The described time preferably was about most 2 hours for being about most 3 hours, and more preferably from about 10 seconds to the longest 1 hour.Being heated to temperature required is not crucial with the fusing wax and the rate of heat addition of removing all water, but practice goes up and be about 20 ℃/min.-60 ℃/min., preferred about 40 ℃/min.-60 ℃/min., more preferably from about 40 ℃/min..
Make the condition of sample experience sufficient to guarantee sample homogeneity then.These conditions can comprise firmly to be shaken or stirs.If the size of sample is enough big and the size of test pool is enough big and durability is enough good, can in test pool, heat and stirring.In enough big pond, can use magnetic stirrer, but shake just enough usually.Perhaps, can transfer in the test pool then at other phial or vessel in heating and stirring sample.
Not necessarily, can in embodiment 1 or embodiment 2, carry out step 3 (a), wherein will be cooled to environmental baseline with constant cooldown rate then through the sample of heating/stirring.If the professional thinks needs, for the sample of being given to be evaluated, heating also is cooled to environmental baseline and can repeats arbitrarily time with the fusing wax and the step of removing all water, and can in test pool, finish, or in other container, finish, the oil that wherein is cooled to environment temperature is transferred in the test pool then.
In the first embodiment, wherein sample is cooled to environment temperature and is cooled to then at 20 ℃ of regulation pour points that are higher than oil and the target temperature that is lower than between 5 ℃ of the oily regulation pour points, even when using the different testing tool of same type, the cooldown rate in per step also should be consistent between sample.
The cooldown rate that is cooled to environmental baseline in the embodiment 1 or 2 can be any speed, as long as it is consistent at sample room.The cooldown rate that is cooled to environmental baseline is preferably about 5-100 ℃/min., preferred 30-50 ℃/min..
In embodiment 1, be cooled to and be higher than 20 ℃ of regulation pour points and be lower than temperature between 5 ℃ of the regulation pour points with certain cooldown rate, preferably to being higher than 10 ℃ of regulation pour points and being lower than temperature between 2 ℃ of the regulation pour points, this cooldown rate can be 20 ℃/min.-60 ℃/min., preferred 40 ℃/min..
In embodiment 1, be cooled to sample 20 ℃ of the regulation pour points that is higher than crude oil and be lower than selected temperature between 5 ℃ of the regulation pour points of crude oil, preferably to 10 ℃ of the regulation pour points that is higher than crude oil and be lower than selected temperature between 2 ℃ of the regulation pour points of crude oil, then, if necessary, make sample through being enough to make sample and test pool stable the waiting period, it typically is 0-500 second, preferred 0-350 second, more preferably 0-100 second.
In second embodiment, wherein from 20 ℃ of the regulation pour points that are higher than crude oil to 5 ℃ of the regulation pour points that is lower than crude oil, preferably carry out the reading of signal in the step of the temperature ranges cooling sample of 2 ℃ of the regulation pour points that is lower than crude oil 10 ℃ of regulation pour points that is higher than crude oil, this cooldown rate also is constant between sample and instrument, and be about 0.1-1 ℃/min., preferred 0.2-0.75 ℃/min., more preferably 0.25-0.50 ℃/min..
Used oil can be to produce required product and make solvent dewaxing or the sample of the actual oil that catalytic dewaxing is feasible.As used in this paper and the claims, term " the dewaxing feedstock oil that is fit to the candidate " refers to satisfy at least the target pour point of crude oil and/or the oil of cloud point, and described crude oil is generally used for producing the formulated product type that obtains mutual relationship.Though this is preferred, is not essential to enforcement of the present invention.For example, if the target pour point of typical crude oil is not higher than-4 ℃ usually, the oil that is used to produce training set so will have-4 ℃ pour point approximately similarly.That is to say, pour point be 0 ℃ or+2 ℃ etc. crude oil will be unaccommodated, but pour point for for example-2 ,-4 ,-8 ,-10 ℃ etc. crude oil will be fit to.As an alternative, the sample of actual oil can be mixed with (spiked with) various waxes with known quantity of known properties, and this reality oil is known not to be contained the residual wax contamination thing and satisfy the target pour point or the cloud point of the oil that is generally used for producing required formulated oil product.Sample through blending, if still satisfy target pour point or cloud point, then can be used for producing the delta sets of signals and be used to prepare formulated oil, determining whether the viscosity of being concerned about of this formulated oil is satisfied, and set up and make delta signal and the selected low temperature viscosity database that is mutually related.
Remaining wax type by including (represent) the widest scope to be predicted in database and concentration will obtain the residual wax contamination thing and measure the most reliable and effective mutual relationship with selected low temperature viscosity.This is because the type and the concentration of remaining wax can influence light scattering efficiency and low temperature viscosity.By from database, omitting sample with FR remaining wax type and concentration, and, the reliability of this mutual relationship is reduced by in database, introducing the special remaining wax type and/or the concentration that can make the gained mutual relationship deviation or distortion occur.
Be repeatability and the reliability of guaranteeing data, those skilled in the art know, make that to have that variable those parameters, measurement and step be consistent be very important, comprise the allotment of final finished.About crude oil itself, it is by solvent dewaxing or WITH CATALYTIC DEWAXING TECHNIQUE dewaxing.Though this is optional shown in embodiment 1, wish and preferred assessed or wait that the crude oil of evaluating with as the potential suitable raw material of producing any given formulated product dewaxes in an identical manner.That is to say, the raw material of catalytic dewaxing should with the raw material ratio of catalytic dewaxing and grouping, and preferably adopt identical Catalytic processes production, and the raw material of solvent dewaxing should with the raw material ratio of solvent dewaxing and grouping, and preferably adopt identical solvent dewaxing process production.The mutual relationship that the present invention produced all is specific for every kind that is considered different allotment.
Therefore, for the formulated product of the like combinations preparation of using adjuvant, the relation of delta signal intensity and selected formulated oil low temperature viscosity is suitable for.Adjuvant, for example change of viscosity index improving agent or pour point depressant is even nominally produce identical final products test result, also cause allotment different.This difference of adjuvant can produce different results, makes oil provide qualified result with a kind of additive combination, and when when adding a kind of different additive combination, the result who provides is just different or provide underproof result.
For visibly different product, even for identical character, should not be used as the standard of this oil of prediction for a kind of oil of specific formulated oil product low temperature viscosity or the mutual relationship that obtains of one group of oil for any specific low temperature viscosity acceptance or rejection, for example, the mutual relationship of oil (for example machine oil) should be as predicting for example standard of automatic transmission fluid.
Similarly, in case adopt a kind of type of cooling, for all crude oil samples that are used to set up database, and all unknown crude oil of estimating for the quilt that is used to produce specific formulated oil finished product, key is to use the identical type of cooling.The preparation material of the size of test pool, test pool, light source, surveying instrument etc. must keep uniformity at sample room as far as possible, to eliminate any variable except that the residual wax contamination thing of crude oil sample.Even heating crude oil temperature, heat time heating time, guarantee inhomogeneity agitating method and be cooled to environmental baseline also should be consistent, to remove any possible source of uncertain variable at sample room.
The instrument that the present invention can use various existing instruments or easily assemble out.The suitable instrument that is used to carry out light scattering measurement comprise Phase Technologies (Richmond, BritishColumbia, PV70 Analyzer Canada) and Hach 2100AN Turbidimeter (Hach Inc., Coloardo).The Other Instruments that is suitable for carrying out light scattering measurement be arbitrarily UV-Vis, Near IR spectrophotometer (for example, Perkin Elmer, Norwalk,
Broadband or narrow band light in the spectrum in UV, visible light and/or the IR wavelength zone can be used as light source, as long as for all crude oil that are used to set up the database evaluation, and all unknown crude oil samples of estimating for the quilt that is used to produce any specific formulated oil finished product, in case behind selected light and the wavelength, this is selected and just keeps constant getting final product.
When evaluation is used to produce the unknown crude oil of specific formulated oil product, have only above-mentioned consistance could make that contained information is reliable in use in the database.
Near infrared light (Near IR), for example wavelength is about 700-1000nm, preferably about 820-900nm is applicable to the sample of maximum kinds, with the interference of avoiding being caused by some samples especially those dark absorption of sample rather than scattering.
In order to ensure can comparing with the measurement of carrying out in another time in the measurement of carrying out sometime with an instrument, and the measurement of carrying out on an instrument can compare with the measurement of carrying out on another instrument, must calibration instrument.Can come alignment light scattering instrument to the signal intensity of known turbidity standard by measuring.The supplier of this standard comprises Hach and GFSChemicals.Instrument signal is interrelated with linear function and given value usually.Interrelated function is applied to the specimen measured signal strengths.
For some instruments, the relation of signal and particle diameter can be in time or instrument change.So, then also should calibrate this effect.This can be in the particle size range of being concerned about (about usually 0.1-10 micron) derive from by measurement and have known, the preferred signal intensity of size particles suspending liquid uniformly and realize.Regulate instrument till the variation relative time or instrument stabilizer of signal with particle diameter.
Calibration instrument is to guarantee the reading unanimity from same instrument, and (read-across) ability is read in contrast reliably between the different instruments of same type, is the technology of knowing and thinks important for the professional in chemical analysis and the analytical technology usually.
Show to determine remaining wax content by at low temperatures signal delta intensity at short notice, it makes allotment person before using crude oil actual production allotment finished product, can determine in real time whether any a collection of crude oil is applicable to the allotment finished product, thereby be sure of that formulated oil will satisfy low temperature viscosity target.It also makes refining person can regulate dewaxing and other operation, is suitable for allocating the raw material of finished product with preparation.It can make refining person regulate on flight distance (on the fly), satisfies the allotment finished product that low temperature viscosity requires thereby the raw material that is produced can be prepared.
A kind of in the feedstock oil grade that most refinery is produced is Bright Stock.This grade is to adopt Catalytic processes (Cat DW) or solvent dewaxing process (SDW) to produce, and this solvent dewaxing process uses the potpourri of solvent such as petrogas or methyl ethyl ketone (MEK) and toluene as dewaxing solvent.
Residual wax contamination may take place in the machine performance that depends on used process conditions and processing unit (plant).As previously mentioned, the crack or the tear of dewaxing filter cloth that can be by being used for SDW technology, or wax contamination takes place by the catalyst selectivity of the branch road (bypassing) in the Cat DW technology, groove (channeling) or difference.
Research evaluation is from several Bright Stock samples of different refineries and employing SDW or Cat DW explained hereafter, with the degree of determining that wax contamination exists, and quantize the difference of sample room about miniature rotational viscosimeter (MRV) the low temperature viscosity of the machine oil that uses this sample allotment.As the example that is used to detect residual wax contamination in the prior art, determine the cloud point (ASTM D2500) of every kind of Bright Stock sample.
As example of the present invention, use and utilize the Phase Technolgy analyser of red visible light to analyze identical sample.Sample was heated about 1 hour in baking oven under 100 ℃, go up cooling 30 minutes, insert in the test pool and in analyser then and analyze at worktable (benchtop).The sample of measuring 0.15ml amount with transfer pipet in the cylindrical shallow sample cup of instrument, the about 1cm of this glass diameter and minute surface is arranged in the bottom.The top of cup and photodetector towards the lid of chamber in open to sample chamber (compartment).The light that sends from the red LED source is drawn towards the center at the bottom of the mirror of sample cup with the oblique angle.If there is not particle to exist in the sample, light is from direct reflection and away from detecting device.If there is particle, they wherein are recorded as the increase of signal intensity to detecting device scattering part light.Temperature by Peltier device control cup.In temperature program(me), purify the sample chamber of sealing with dry gas.In analytic process, adopt following Temperature Distribution.
Distribution table B
| Step | The beginning temperature, ℃ | Finishing temperature, ℃ | Speed, ℃/minute | Soaking (soak), second | |
| | Environment temperature | 60 | 40 | 10 | |
| | 60 | 20 | 40 | 0 | |
| | 20 | 60 | 40 | 10 | |
| | 60 | 0 | 40 | 1800 |
Begin the time of ionization meter (Sec.) first from steps A: 350 (after among step D, reaching 0 ℃ about 60 seconds)
Distribution table D
| Step | The beginning temperature, ℃ | Finishing temperature, ℃ | Speed, ℃/minute | Soaking, second | |
| | Environment temperature | 60 | 40 | 10 | |
| | 60 | 20 | 40 | 0 | |
| | 20 | 60 | 40 | 10 | |
| | 60 | 8 | 40 | 1800 |
Begin the time of ionization meter (Sec.) first from steps A: 350 (after among step D, reaching 8 ℃ about 72 seconds)
Each sample at first is heated to 60 ℃ and kept 10 seconds under this temperature, is cooled to 20 ℃ then.Be heated to 60 ℃ and under this temperature, kept 10 seconds again with being about to sample after this.The purpose of initial heating step is to destroy the effect of the thermal history of the sample that can influence wax crystallization speed and analysis result.Sample is cooled to 0 ℃ or 8 ℃ (respectively referring to distribution table B and D, step (D)) behind the heating steps.After each sample reached target temperature (0 ℃ or 8 ℃), be 60-72 second stationary phase, afterwards, and by of the first measurement of analyser record to the light intensity of scattering from sample.Also write down the final strength of scattered light when the end of 30 minutes soaking period.First and the difference between the final strength value be recorded as delta intensity (DI) parameter, the main result that it is to use the PhaseTechnology analyser to analyze.
The suitable Temperature Distribution that selection is used to analyze depends on the type of sample and is used to produce its technology.Final soaking temperature must be enough low, grow up to can be (for example with the crystal that promotes the residual wax contamination composition at rational soaking time, 30 minutes) the interior detected reliably degree of analyzed instrument, but not too low so that the crystal from the acceptable wax (that is, not being the wax contamination composition) of normal presence is grown up will be promoted and add/influence the DI value that sample is determined.In the present embodiment, find that distribution table B (0 ℃/30 minutes) is suitable for the particular B right Stock sample by the SDW explained hereafter, and distribution table D (8 ℃/30 minutes) is suitable for the particular B right Stock sample by Cat DW explained hereafter.Use these two distribution table analyses to be included in the various samples of the Bright Stock in this research; According to the viscosity grade of other raw material and be used to produce their dewaxing technique, other distribution table will be suitable for other raw material.
Use the various samples of identical Bright Stock, adopt the fixed standard number percent of composition separately, prepare the potpourri of 20W50 machine oil respectively.When this a series of potpourri of preparation, only change Bright Stock composition (source); The same physical sample that the oil of every volume comes the remaining wax content of self-test to use, and use the fixed percentage of every kind of other composition to prepare every kind of potpourri.Table 1 has been summarized the mensuration of the DI/ cloud point of each used in the character of machine oil potpourri and potpourri Bright Stock sample.In Fig. 1, the miniature rotational viscosimeter result of 20W50 potpourri draws as the function of the cloud point of Bright Stock composition separately.This diagram shows be used for detecting the prior art of crude oil wax content.These results show that the cloud point of Bright Stock composition is insecure indication of the MRV of corresponding machine oil.Obviously, take place in can be in this research observed whole cloud point scope of unacceptable height (defective) MRV result, and can not determine so clear and definite cloud point, be higher than this and name a person for a particular job and underproof MRV result occurs.
In Fig. 2, the MRV result of 20W50 potpourri draws as the function of delta intensity (DI) value that Bright Stock composition is separately determined.Compared to Figure 1, this figure shows that the interrelated of DI value and MRV result is greatly improved.According to the result of Fig. 2, as if it is about 4.0 needing the DI maximal value for raw material, is no more than greatest limit with the MRV that guarantees corresponding machine oil.Compared to Figure 1 the result of Fig. 2 has illustrated the improvement that the present invention is obtained compared to existing technology.
Table 1
Bright Stock quality is for the influence based on the low temperature viscosity of the 20W-50 of multiple Bright Stock sample
| Sample | A | C | D | E | F | G | H | I | |||
| 40 ℃ of the neutral light feedstock oil wt% performance additive wt% test result KV of dewaxing technique (I) Bright Stock wt%, 100 ℃ of cSt KV, the cSt pour point, ℃ CCS-15 ℃, cP MRV-20 ℃, cP MRV yield stress-20 ℃, 0 ℃ of Pa Delta intensity (DI) Bright Stock composition, 30 minutes 8 ℃, the cloud point of 30 minutes Bright Stock compositions | Minimum 18.0 | Maximum 20.0-15 ℃ 9,500 60,000＜35 | D445 D445 D97 D5293 D4684 D4684 D2500 | Cat DW 37.96 46.14 15.9 177.6 19.34 -17 9000 27900 ＜35 21.5 3.8 0 | PDU 37.96 46.14 15.9 177.4 19.04 -20 8530 25013 ＜35 0 0 -3 | Cat DW 37.96 46.14 15.9 180.6 19.32 -18 9070 ＞400000 ＜350 60.6 12 1 | Cat DW 37.96 46.14 15.9 176.4 19.06 -20 9020 45117 ＜35 18.2 1.9 -2 | Cat DW 37.96 46.14 15.9 177.8 19.21 -19 8800 ＞400000 ＜280 70.9 11.8 -2 | Cat DW 37.96 46.14 15.9 179.6 19.14 -21 8450 57368 ＜70 9.9 1.7 -4 | Cat DW 37.96 46.14 15.9 179.1 19.12 -17 8510 24100 ＜35 10.5 1.7 -6 | Cat DW 37.96 46.14 15.9 176.3 18.92 -17 8850 ＞400000 ＜280 85.7 9.8 4 |
Table 1 (continuing)
Bright Stock quality is for the influence based on the low temperature viscosity of the 20W-50 of multiple Bright Stock sample
| Sample | J | L | M | N | O | P | Q | |||
| 40 ℃ of the neutral light feedstock oil wt% performance additive wt% test result KV of dewaxing technique (I) Bright Stock wt%, 100 ℃ of cSt KV, the cSt pour point, ℃ CCS-15 ℃, cP MRV-20 ℃, cP MRV yield stress-20 ℃, 0 ℃ of Pa Delta intensity (DI) Bright Stock composition, 30 minutes 8 ℃, the cloud point of 30 minutes Bright Stock compositions | Minimum 18.0 | Maximum 20.0-15 ℃ 9,500 60,000＜35 | D445 D445 D97 D5293 D4684 D4684 D2500 | Cat DW 37.96 46.14 15.9 172.2 18.64 -17 8390 26100 ＜35 30.6 0.2 0 | Cat DW 37.96 46.14 15.9 173.1 18.73 -20 8760 27800 ＜35 58.1 2.4 -10 | Cat DW 37.96 46.14 15.9 175 18.89 -15 8830 177810 ＜140 84.4 6.7 -10 | PDU 37.96 46.14 15.9 174.6 19.15 -17 7830 24815 ＜35 0.2 0.4 -7 | MEK/Tol 37.96 46.14 15.9 178.1 19.19 -18 8820 24900 ＜35 0.1 0.0 -2 | PDU 37.96 46.14 15.9 176.1 18.93 -28 8390 24805 ＜35 0.6 0.9 -5 | MEK/Tol 37.96 46.14 15.9 174.6 19.09 -21 8430 24910 ＜35 0.4 0.0 -8 |
(1) dewaxing technique abbreviation: Cat DW: catalytic dewaxing; PDU: propane dewaxing unit; The dewaxing of MEK/Tol:MEK/ toluene solvant.
Utilize temperature ramp control to use MRV in the 20W-50 machine oil of 2500SUS feedstock oil
Use with embodiment 1 in sample among the identical device to test embodiment 1, but employing temperature ramp rather than constant temperature soaking period among the embodiment 2.The define objective pour point of these feedstock oils is-6 ℃.Sample was kept 1 hour down at 100 ℃, commoves then, sample is placed test pool and experiences following temperature program(me):
| Step | The beginning temperature, ℃ | Finishing temperature, ℃ | Speed, ℃/minute | In the time that finishing temperature keeps, second | |
| | Environment temperature | 20 | 40 | 1800 | |
| | 20 | 60 | 40 | 10 | |
| | 60 | 20 | 40 | 0 | |
| | 20 | 60 | 40 | 10 | |
| | 60 | 14 | 40 | 10 | |
| F | 14 | -2 | 0.25 |
Beginning temperature in the steps A refers to the temperature of test pool.Just before putting into test pool sample temperature near 100 ℃.
The temperature cycles order of step B and C is not mandatory step, but the wax in the sample of help further reduction liquid water content and the very fast change blushing of dissolving.Do not use other stationary phase after the step e in this case, because temperature ramp begins under the temperature that takes place far above crystallization.
In this experiment, wherein temperature fades to-2 ℃ from 14 ℃ in the embodiment 2, and available various parameters and MRV are interrelated, comprise initial threshold (onset threshold), promptly reach the temperature that little constant signal increases, reach the temperature of big delta signal, its combination and variation thereof.Therefore, the temperature that selected low temperature viscosity can be when reaching given signal delta intensity and interrelated to the combination in any of delta intensity under the fixed temperature.Can use the statistical method of knowing for this purpose, for example multiple linear regression, principal component regression (principle componentregression) and partial least square method are analyzed.Referring to, for example, " MultivariateCalibration ", Harald Martens and Tormod Naes, John Wiley and Sons, 1989.Fig. 3 has shown in this temperature ramp process the signal from 4 samples.
Shown the difference between 14 ℃ signal when the signal of 10 ℃, 6 ℃ and-2 ℃ and temperature ramp begin in the table.In these temperature, provide best interrelated with MRV at 6 ℃ signals.Need low MRV viscosity and yield stress in the formulated oil.Can use this temperature ramp, short temperature ramp (for example, 14 ℃ to 6 ℃) near or at 6 ℃ constant temperature and there is soaking (as in embodiment 1) to form all database.Use is related well with MRV at the delta signal at 8 ℃ constant temperature described in the embodiment 1.Can use standard statistical routines to select best light scattering or transmittance parameter or parameter combinations.
In the present embodiment, used optimum temperature is so to be higher than target pour point (+6 ℃ of vs.-6 ℃ of pour points), and this is beat all.Temperature ramp is used for determining suitable temperature or temperature range fast, and is interrelated to be used to form.
| Sample number | O | G | H | F | E | A |
| MRV@-20 ℃ of yield stress, Pa,＜35 | ＜35 | ＜70 | ＜35 | ＜280 | ＜35 | ＜35 |
| MRV@-20 ℃, viscosity, cP, 55600 | 24900 | 57638 | 24100 | ＞400000 | 45117 | 27900 |
| DI@10℃ | 0.1 | 0.0 | -0.1 | 0.1 | 0.0 | 0.1 |
| DI@6℃ | 0.2 | 0.9 | 0.0 | 3.3 | 0.4 | 0.7 |
| DI@-2℃ | 0.4 | 7.4 | 9.9 | 30.6 | 11.6 | 30.6 |
| Sample number | Q | P | N | M | J | L | I |
| MRV@-20 ℃ of yield stress, Pa | ＜35 | ＜35 | ＜35 | ＜140 | ＜35 | ＜35 | ＜280 |
| MRV@-20 ℃, viscosity, cP | 24910 | 24805 | 24815 | 177810 | 26100 | 27800 | ＞400000 |
| DI@10℃ | -0.1 | 0.0 | -0.1 | 0.0 | 0.1 | 0.1 | 3.5 |
| DI@6℃ | -0.1 | 0.0 | -0.1 | 1.7 | 0.3 | 1.1 | 12.0 |
| DI@-2℃ | -0.1 | 0.1 | -0.2 | 34.0 | 16.3 | 16.8 | 45.8 |
MRV in the 20W-50 machine oil of the main use of control 600SUS feedstock oil
Product certification needs the MRV viscosity and the yield stress of machine oil to be lower than setting.A kind of such prescription contains the conventional feedstock oil of 600SUS (nominally be 600 Saybolt universal seconds at 100 ) of 67wt%.The target pour point of these feedstock oils is-6 ℃.Except using different 600SUS samples, with identical performance additive composition mixing preparation oil.Those samples have identical pour point.But, formulated oil MRV yield stress and viscosity difference.Adopt with embodiment 1 and 2 in used identical instrument come specimen.Oil is heated and remain on 100 ℃ to descend about 1 hour, in baking oven, in phial, heat with sample.After heating and the stirring, sample is placed test pool.Sample adopts about 74 seconds stabilization time after reaching-4 ℃, and when the constant temperature that adopts-4 ℃ among the final 3600 seconds soak step E in the following temperature program(me) of embodiment 1, following table shown, DI and MRV's is good interrelated.In this case, in final soak step, adopt 0 ℃ temperature and the time of 1800sec, and the stabilization time of 60sec, performance do not damaged.
| Step | The beginning temperature, ℃ | Finishing temperature, ℃ | Speed, ℃/minute | In the time of finishing temperature soaking, second | |
| | Environment temperature | 20 | 40 | 1800 | |
| |
20 | 60 | 40 | 10 | |
| |
60 | 20 | 40 | 0 | |
| |
20 | 60 | 40 | 10 | |
| E | 60 | -4 | 40 | 3600 |
Begin the time (Sec.) that initial strength is measured: 2170 (about 74sec after step e, reaching-4 ℃) from steps A
| Sample | Pour point (D97), ℃ | No pour point (D5985), ℃ | At the yield stress of-20 ℃ of following MRV, Pa (1) | At the viscosity of-20 ℃ of following MRV, centipoise (2) | DI (0 ℃ of soaking) | DI (-4 ℃ of soaking) |
| 1 | -6 | -6 | ＜35 | 36228 | 0 | 16.4 |
| 2 | -6 | -6 | ＞140 | 57400 | 0 | 75.6 |
| 3 | -6 | -7 | ＜35 | 33400 | 0.1 | 4.7 |
(1) the MRV yield stress target for formulated oil is＜35Pa@-20 ℃
(2) be≤60-20 ℃ of MRV viscosity targets for formulated oil, 000cP
Therefore,, reach lower DI at-4 ℃ about 20 and be relevant to best by 60 for this allotment under described test condition for these oil, the low temperature viscosity target regulation of 000cP peak viscosity reaches the maximum yield stress at-20 ℃ of time＜35Pa.
Utilize the MRV in the 20W-50 machine oil (prescription 1) of the main 600SUS of use of temperature ramp control feedstock oil
Use as used identical instrument among the embodiment 1,2 and 3, and temperature ramp in the embodiment 2 rather than constant soaking temperature, the sample among the top embodiment (embodiment 3) tested.Before putting into test pool, oil samples is heated to 100 ℃ temperature and kept about 1 hour in phial.
| Step | The beginning temperature, ℃ | Finishing temperature, ℃ | Speed, ℃/minute | In the time of finishing temperature, second | |
| | Environment temperature | 20 | 40 | 1800 | |
| | 20 | 60 | 40 | 10 | |
| | 60 | 20 | 40 | 0 | |
| | 20 | 60 | 40 | 10 | |
| | 60 | 2 | 40 | 10 | |
| F | 2 | -8 | 0.25 |
Available a plurality of parameter is controlled MRV, comprises initial threshold, reaches temperature that given signal strengthens, and strengthening to the signal under the fixed temperature.Initial threshold used herein is the temperature that DI reached 0.5 o'clock.Shown in Figure 5 is through measuring and the related value of MRV at the DI grade and the dotted line at temperature place.All in this case parameters can be distinguished different behaviors.Preferred in this case parameter is the DI increase at-5 ℃.Fig. 5 shown for 3 kinds of oil of being surveyed, when temperature when 0 drops to-8 ℃, the relation curve of DI and temperature.In this case, by from the intensity of lower subsequently temperature measuring, deducting intensity, thereby determine the DI value, just established 0 intensity baseline 0 ℃ intensity 0 ℃ of mensuration.
Listed formulated oil low temperature viscosity below, and the DI increase with-5 ℃ is associated to every kind of oil for three kinds of oil.
| Sample | At the yield stress of-20 ℃ of following MRV, Pa | At the viscosity of-20 ℃ of following MRV, centipoise | Initial temperature, ℃ | Reach the temperature of 20DI, ℃ | Increase at-5 |
| 1 | ＜35 | 36200 | -2.7 | -6.2 | 9.2 |
| 2 | ＞140，＜175 | 57400 | -2.0 | -3.5 | 84.2 |
| 3 | ＜35 | 33400 | -4.6 | -6.6 | 1.7 |
Therefore, for these oil that should prescription under described test condition ,-5 ℃ up to 9.2 but be associated most with the qualified of being concerned about of MRV cryogenic properties less than 84.2 DI.Comparative example 3 and embodiment 4, both all use identical oil sample, appear as to make interrelated meaningfully with DI value, must test (test condition of sample room must unanimity) in an identical manner to every kind of oil sample.Therefore, can not come the data of application implementation scheme 1 generation with respect to the database that uses embodiment 2 to produce, vice versa.Handle with specimen in consistance be necessary, can be used for any database that provides to guarantee the gained data, processing that applies to any sample and test be used the same of generation database.That is to say to have only the program of the embodiment 1 by being used to produce database that unknown sample is carried out outer reason and test, use information in the database that embodiment 1 produces to be only useful and can provide significant information about unknown sample.As the same for producing databases with embodiment 2, the program of embodiment 2 that must be by being used to produce database is carried out outer reason and test to unknown sample.
Utilize the MRV in the main 20W-50 machine oil (prescription 2) that uses 600 SUS feedstock oils of temperature ramp control
In 20W-50 second machine oil that mainly uses 600SUS feedstock oil, test from the sample in embodiment 3 and 41 and 3, and two other sample, sample 4 and 5, but the formulated oil employing in this case and the 1 different pour point depressant of filling a prescription.Use with embodiment 1,2 and 3 in identical instrument and use with embodiment 4 in identical temperature ramp come specimen.Identical with embodiment 4, before putting into test pool, sample is heated to 100 ℃ temperature and kept about 1 hour in phial.
In the present embodiment, when sample 1 was mixed in the 20W50 machine oil, MRV test was defective for criticality because its yield stress be＞35Pa still＜70Pa, and requirement is＜35Pa.Sample 3 meets the demands.Sample 4 in this test for seriously defective because its yield stress＜280Pa still＞245Pa, and it is also satisfied≤60, the viscosity requirement of 000cP.Sample 5 is border property, and is qualified but defective in another repeated test in a test.
In the present embodiment, initial temperature is related bad with MRV's, because serious underproof sample 4 is lower than the initial temperature of the underproof sample 1 of criticality.Referring to Fig. 6.For these oil that should prescription under described test condition ,-5 ℃ up to 0.2 but be associated with the qualified of being concerned about of MRV cryogenic properties less than about 1.7 DI.With present embodiment and embodiment 4 relatively, obviously draw and the qualified/defective DI ultimate value that be associated of formulated oil, need change along with the change of the prescription of wherein measuring cryogenic properties about the selected low temperature viscosity be concerned about.By being adjusted in the interrelated of the DI that takes place among the step b6 with the step b10 of embodiment 1 or embodiment 2, this method will provide prediction accurately.
| Sample | No pour point (D5985), ℃ | The yield stress of MRV in the time of-20 ℃, Pa (1) | The viscosity of MRV in the time of-20 ℃, centipoise (2) | Initial temperature, ℃ | Reach the temperature of 20DI, ℃ | DI in the time of-5 ℃ increases |
| 1 | -6 | ＜70 | 34400 | -2.7 | -6.2 | 9.2 |
| 3 | -7 | ＜70；＜35 | 3400， 33600 | -4.6 | -6.6 | 1.7 |
| 4 | ＜280 | 68500 | -3.0 | -4.9 | 22.3 | |
| 5 | -7 | ＜35 | 38100 | -5.4 | -8.2 | 0.2 |
(1) the MRV yield stress target for formulated oil is＜35Pa@-20 ℃
(2) be≤60-20 ℃ of MRV viscosity targets for formulated oil, 000cP
Control with the MRV in the machine oil (5W-30) of the neutral light feedstock oil allotment of Group II
Product certification needs the MRV viscosity and the yield stress of machine oil to be lower than setting.A kind of such prescription contains the 120SUS Group II feedstock oil of 82wt%.The target pour point of these feedstock oils is-18 ℃.Except using different 120SUS feedstock oil, with identical performance additive composition mixing preparation oil.Feedstock oil has identical cloud point and pour point, and usually superperformance is guaranteed in use test, and it is identical therefore to be expected in the low-temperature test performance.But the MRV behavior of the lubricating oil that mixes with these two kinds of feedstock oils is very different.
Use the instrument identical with previous embodiment.
Following table has shown the temperature ramp that uses embodiment 2, and DI and MRV's is good interrelated.Before introducing test pool, oil samples is heated to 100 ℃ temperature and kept about 1 hour in phial.
| Step | The beginning temperature, ℃ | Finishing temperature, ℃ | Speed, ℃/minute | In the time of finishing temperature soaking, second | |
| | Environment temperature | 20 | 40 | 1800 | |
| | 20 | 60 | 40 | 10 | |
| | 60 | 20 | 40 | 0 | |
| | 20 | 60 | 40 | 10 | |
| E | 60 | -8 | 40 | 10 | |
| F | -8 | -22 | 0.25 |
Available a plurality of parameter is controlled MRV, comprises initial threshold, reaches temperature that given signal strengthens, and strengthening to the signal under the fixed temperature.These all in this case parameters can be distinguished different behaviors.Preferred in this case parameter is the DI increase at-19 ℃.Fig. 7 has shown the neutral light crudes for two kinds of Group II, when temperature when-14 ℃ drop to-22 ℃, the relation curve of signal intensity (DI) and temperature the figure illustrates the variation between-15 ℃ to-21 ℃.
| Sample | Pour point (D5950), ℃ | Cloud point (D2500), ℃ | The yield stress of MRV in the time of-35 ℃, Pa (1) | The viscosity of MRV in the time of-35 ℃, centipoise (2) | Initial temperature, ℃ | Reach the temperature of 20 DI, ℃ | DI in the time of-19 ℃ increases |
| 6 | -18 | -13 | ＜35 | 18600 | -17.9 | -20.0 | 5.7 |
| 7 | -18 | -13 | ＜35 | 98500 | -16.8 | -17.9 | 74.4 |
(1) the MRV yield stress target for formulated oil is＜35Pa@-20 ℃
(2) be≤60-35 ℃ of MRV viscosity targets for formulated oil, 000cP
Cloth network gram Field viscosity in the control hydraulic oil
For the performance of the best, wish in some applications that the cloth network gram Field viscosity maintenance of hydraulic oil is minimum.This oil contains the 100SUS feedstock oil of 59wt%.The target pour point of these feedstock oils is-18 ℃.Except the wax that adds variable wax undesirably leaks in the feedstock oil in the production run of refinery with simulation, with identical performance composition hydraulic hybrid oil.All compositions were mixed 1-2 hour down at 100 ℃, to guarantee complete dissolving wax.Use the instrument identical with previous embodiment.Following table has shown, adopts as embodiment 3 described temperature program(me)s, uses-4 ℃ constant temperature in the final soak step that the DI that is adopting embodiment 1 measures, and the relevance of DI and cloth network gram Field viscosity is good.
| % wax | DI (-4 ℃ of following soaking) | At-30 ℃ Brookfield viscosity, |
| 0 | 0 | 2320 |
| 0.3 | 0 | 2380 |
| 0.6 | 4.8 | 2460 |
| 1.0 | 45.0 | 2760 |
For oil product, be maximum 2800cP-30 ℃ of cloth network gram Field viscosity targets.Therefore, the DI value is about 45 display performances general (marginal), but the DI value is preferably about 5 or more hour less than 45, and is functional.
Control automatic transmission and restrain Field viscosity with the cloth network in the oil
For the performance of the best, wish in some applications that the cloth network gram Field viscosity maintenance of hydraulic oil is minimum.The ATF oil of being studied contains the 100SUS feedstock oil of 57wt%.The target pour point of 100SUS feedstock oil is-18 ℃.Except the wax of intentional interpolation variable wax undesirably leaks in the feedstock oil in the production run of refinery with simulation, with identical performance additive composition hydraulic hybrid oil.All compositions were mixed 1-2 hour down at 100 ℃, to guarantee complete dissolving wax.Use the instrument identical with previous embodiment.Following table shown, when using-4 ℃ constant temperature in the final soak step that the DI that is adopting embodiment 1 measures (temperature program(me) identical with embodiment 3), DI is good with the relevance that the cloth network restrains Field viscosity.
| % wax | DI (-4 ℃ of soaking) | At-40 ℃ cloth network gram Field viscosity, |
| 0 | 0 | 13320 |
| 0.1 | 0 | 13360 |
| 0.3 | 0 | 13560 |
| 0.6 | 4.8 | 13920 |
| 1 | 45.0 | 19700 |
For this oil product, be maximum 20-40 ℃ of cloth network gram Field viscosity targets, 000cP.Therefore, as other sample shown in-4 ℃, the DI value be about 45 show by the performance of the product of oil samples allotment general, but the DI value is preferably about 5 or more hour less than 45, functional.
With the hydraulic oil of embodiment 7 and identical with the grade of the qualified DI value that is associated of ATF performance of embodiment 8, this only is a coincidence.Generally speaking, adjuvant and associating feedstock oil (co-basestock), and the type of low-temperature test, temperature and other conditions all will influence and be reflected in the difference of accurate DI grade and temperature, measure under this temperature to guarantee satisfying the sticky parameter target for dissimilar formulated oil products.
Claims (15)
1. method, this method are used for determining in real time whether feedstock oil is suitable for use as produces the raw material that satisfies the full formulated oil that product low temperature viscosity requires, and this method comprises:
(a) at least one low temperature viscosity of the full formulated oil of selection;
(b) produce training set through the following steps:
(1) sample of acquisition dewaxing feedstock oil;
(2) the feedstock oil sample is heated sufficiently long time and be heated to sufficiently high temperature, so that the wax in the sample all melts;
(3) sample of stirring through heating is to guarantee homogeneity;
(4) in sample cell oil is cooled to and is being higher than 20 ℃ of crude oil regulation pour points and is being lower than temperature between 5 ℃ of the crude oil regulation pour points, described sample cell is equipped with the heating and cooling device, and is provided for measuring reflection of light or the optical transmission that produces from the source;
(4a) wait for that sample and test pool settle out;
(5) later under the temperature of step 4, measure scattering/reflected light stationary phase or pass the signal of the transmitted light of sample, to obtain the first intensity reading;
(6) sample was kept 1 minute to 3 hours under the temperature of step 4;
(7) signal of measuring scattering/reflected light or transmitted light when retention time of step 6 finishes to be obtaining the second intensity reading, and measures any variation (signal delta intensity) of the signal intensity between the first signal reading and secondary signal reading;
(8) use feedstock oil formulated oil product, and selected low temperature viscosity in the mensuration step (a) relevant with product quality;
(9) as required, use to be higher than 20 ℃ of regulation pour points and to be lower than different temperatures repeating step 1-8 between 5 ℃ of the regulation pour points, until the relation of observing signal delta intensity and selected selected low temperature formulated oil viscosity;
(10) make signal delta intensity and selected low temperature viscosity interrelated;
(c) make crude oil experience step 1-8;
(d) signal delta intensity and the Relational database with crude oil in the step (c) compares, and whether available described crude oil prepares the formulated oil with selected low temperature viscosity with prediction.
2. method, this method are used for determining in real time whether feedstock oil is suitable for use as produces the raw material that satisfies the full formulated oil that product low temperature viscosity requires, and described method comprises:
(a) at least one low temperature viscosity of the full formulated oil of selection;
(b) produce training set through the following steps:
(1) obtains the sample of dewaxing feedstock oil to be used to produce full formulated oil;
(2) feedstock oil is heated sufficiently long time and be heated to sufficiently high temperature, so that the wax in the sample all melts;
(3) sample of stirring through heating is to guarantee homogeneity;
(4) put about 20 ℃ and put about 5 ℃ to being lower than the fuel oil meter constant inclination from being higher than the fuel oil meter constant inclination, in sample cell sample is slowly cooled off, described sample cell is equipped with the heating and cooling device, and is provided for measuring reflection of light or the optical transmission that produces from the source; Measure reflect/scatter or transmission signal, and measure the ongoing variation of signal intensity (signal delta intensity) in the described cooling procedure;
(5) oil that feedstock oil is produced is used in allotment, and selected low temperature viscosity in the measurement step (a) relevant with product quality;
(6) make signal delta intensity and selected low temperature viscosity interrelated;
(c) make crude oil experience step 1-4;
(d) signal delta intensity and the Relational database with crude oil in the step (c) compares, and whether available described crude oil prepares the formulated oil with selected low temperature viscosity with prediction.
3. method according to claim 1 and 2, wherein, heating steps (b) (2) is with time enough and is heated to sufficiently high temperature, so that the wax in the sample all melts and removes all water that exists in the sample.
4. method according to claim 1 and 2 wherein, is implemented cooling step 3 (a), thereby sample is cooled to environmental baseline, and the cooldown rate that is cooled to environmental baseline is 5 ℃/min.-100 ℃/min..
5. method according to claim 1, wherein, being cooled to sample in the cooldown rate that is higher than 20 ℃ of crude oil regulation pour points and is lower than the temperature between 5 ℃ of the crude oil regulation pour points is 20 ℃/min.-60 ℃/min..
6. method according to claim 1, wherein be 0-600 second the stationary phase of step (4a).
7. method according to claim 1, wherein the retention time of step (b) (6) is about 30-90 minute.
8. method according to claim 1 and 2, wherein reflection or transmitted light are at ultraviolet, visible light or the infrared wavelength region of spectrum.
9. method according to claim 1, wherein, make one or more extra samples of identical or different dewaxing feedstock oil experience step (b) respectively (1-9), to obtain for multiple crude oil sample the database of the mutual relationship of signal delta intensity and selected formulated oil low temperature viscosity.
10. method according to claim 2, wherein, make one or more extra samples of identical or different dewaxing feedstock oil experience step (b) respectively (1-5), to obtain for multiple crude oil sample the database of the mutual relationship of signal delta intensity and selected formulated oil low temperature viscosity.
11. method according to claim 2 wherein, is 0.1 ℃/min.-1 ℃/min. being higher than 20 ℃ of the crude oil regulation pour points cooldown rate of sample in the temperature range that is lower than between 5 ℃ of the crude oil regulation pour points.
12. method according to claim 1 and 2, wherein, low temperature viscosity is selected from miniature rotational viscosimeter (MRV) viscosity and yield stress, cloth network gram Field viscosity, cold start simulation (CCS), pour point.
13. method according to claim 2, the temperature (initial temperature) when wherein selected low temperature viscosity and signal intensity begin to strengthen is interrelated.
14. method according to claim 2, the wherein selected low temperature viscosity temperature when reaching given signal delta intensity is interrelated.
15. method according to claim 2, the interrelated temperature when reaching given signal delta intensity of wherein selected low temperature viscosity with in combination in any to the delta intensity under the fixed temperature.
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| CN101675332B (en) * | 2007-05-02 | 2011-04-06 | 国际壳牌研究有限公司 | Method for predicting a physical property of a residue obtainable from a crude oil |
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