CN1017186B - Rapid determination of asphaltene content and device therefor - Google Patents
Rapid determination of asphaltene content and device thereforInfo
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- CN1017186B CN1017186B CN 87101666 CN87101666A CN1017186B CN 1017186 B CN1017186 B CN 1017186B CN 87101666 CN87101666 CN 87101666 CN 87101666 A CN87101666 A CN 87101666A CN 1017186 B CN1017186 B CN 1017186B
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Abstract
The present invention relates to a method and a used instrument thereof for measuring the asphaltine content in heavy hydrocarbon oil. The method comprises: the absorbency of a test solution containing dispersed asphaltine particles to two light waves selected from the wavelength range of about 300 to 1000 nanometers is measured, and the content of asphaltine is calculated from the measuring value by utilizing relation between the known content of asphaltine and the absorbency. The instrument device comprises an immersion detector or a flow cell, a dual-wavelength absorbency detector and a computer, wherein the immersion detector can be immersed in test solutions, the flow cell enables test solutions to flow in the flow cell, the dual-wavelength absorbency detector detects the absorbency of test solutions to two different light waves and converts the absorbency into a current value, and the computer converts the current value into the content of asphaltine.
Description
The present invention relates to the method for fast measuring such as long boiling range residual oil, short boiling range residual oil, hydrocrackates, hot tearing carburetion, oil shale fuel, oil-sand wet goods heavy hydrocarbon oil medium pitch matter content, and relate to the instrument that carries out said determination automatically.
Asphalt content in the heavy hydrocarbon oil is not only the sign of heavy hydrocarbon oil combustibility and bin stability, but also is a key factor that influences catalytic activity in the direct desulfurization process greatly.Therefore, need measure the asphalt content in the heavy hydrocarbon oil rapidly and accurately according to the control of product and conditions for process control.
Usually measure asphalt content (being the weight content of bituminous matter) according to the method (IP143 is hereinafter to be referred as the IP method) of petroleum institute.The IP method comprises sample is dissolved in the warm normal heptane of ormal weight, potpourri with the filter paper filtering generation, the insolubles of being collected by filtration with heptane backflow washing in Soxhlet extractor is in this extractor, with the dissolved matter of toluene extracting insolubles and the extracting of mensuration institute.Yet, because the IP method comprises complicated operations and need reach nine hours analysis time, so partly (UOP 614/80 by the method for Universal Oil Products Company, hereinafter to be referred as the UOP method) replace, in the method, filter the sample in the warm normal heptane be dissolved in ormal weight with membrane filter, and the insolubles of collecting on the filter is measured as asphalt content.Yet the UOP method still needs about 4 hours analysis time, and measured value and be not inconsistent with the value of IP method gained.Therefore, need a kind of simple and rapid of development to measure bitum method, make the value and the IP value that record in full accord.
The rapid test method of the asphalt content of Tui Jianing comprises (1) Ono method (Tastuo Ono so far, Petroleum Association of Japan's meeting will, the 14th volume, No. 9,504(1971)), (2) (people such as Tsutomu Kaibara is published in " Petroleum Association of Japan can will " to absorptionmetry, the 23rd volume, No. 3,178(1980)) and people such as Michel Bouquet be published in " fuel ", the 64th volume, 1625(1985)), and (3) hydrogen flame ionization detects thin-layered chromatography (FID-TLC), and (Marc-And ' people such as re Poirier are published in " chromatographia meeting will " the 21st volume, No. 9,331(1983) and people such as Yojiro Yamamoto be published in " Petroleum Association of Japan can will ", the 27th volume, No. 3,269(1984)).
Except saving toluene extraction, the included step of Ono method is identical with the IP method, and it is substantially identical with the UOP method with measured value to analyze required time.
People's such as Yamamoto hydrogen flame ionization detects thin-layered chromatography and comprises the test solution point sample on the silica gel thin-layer rod, launches test solution with a kind of solvent (as toluene), isolates bituminous matter, and measures asphalt content with flame ionization detector.Though this method successfully makes measured value corresponding with the IP value, and make the analysis required time reduce to per 10 samples and need 30 to 60 minutes, but this method has shortcoming, because in whole measuring process, the analyst should observe measuring system always, and its analytical precision depends on unfolding condition to a great extent, so cause poor reproducibility.
People's such as Kaibara absorptionmetry comprises sample is dissolved in normal heptane, with the absorbance of spectrophotometric determination solution to 700 millimicrons of light waves, further measure by solution and filter the absorbance of gained filtrate 700 millimicrons of light waves, difference from solution filtration front and back absorbance obtains asphaltene concentration.According to this method, reduced to required analysis time about 30 minutes.Yet, the filter operation complexity, though its measured value is relevant with the IP value, its related coefficient is 0.979, and is lower than general acceptable related coefficient (promptly being not less than 0.99).
According to people's such as Michel method, sample is dissolved in the toluene, and measures the absorbance of solution 750 millimicrons of light waves.Under constantly stirring, normal heptane is added in another sample of getting in addition from identical oil plant, by filtering the bituminous matter of precipitation is removed.Use normal heptane to compare liquid, measure gained not the solution of asphaltenes to the absorbance of 750 millimicrons of light waves.Then, try to achieve asphaltene concentration by the difference of two solution absorbances.It is heavy up to 40%(that this method can be measured concentration) bituminous matter, but still need complicated filter operation.
One of purpose of the present invention provides the bitum method of a kind of mensuration, compares with conventional process, can measure the bituminous matter of concentration range broad more quickly by this method.
Another object of the present invention provides the bitum method of a kind of mensuration, by this method, and can be accurately and analyze some samples apace and do not need filter operation.
Further purpose of the present invention provides a kind of instrument that above-mentioned bituminous matter is measured that carries out.
Find at present, above-mentioned purpose can be by asphaltene precipitation being prepared sample method and the method for dual wavelength absorptiometry combine, and by using the analyzer system that forms by defeated sample device, two-wavelength absorption photometric detector and microcomputer to finish.
Fig. 1 is that test solution reaches the absorption spectrum of test solution in visible region that has filtered.
Fig. 2 is the automatic analyzer synoptic diagram according to dipping detection system of the present invention.
Fig. 3 is a dual wavelength absorption photometric detector enlarged diagram used in Fig. 2 instrument.
Fig. 4 is the automatic analyzer synoptic diagram according to flow cell of the present invention system.
Therefore, total target according to the present invention provides a kind of method of measuring the asphalt content in the heavy hydrocarbon oil, this method comprises the test solution of measuring the asphalitine particle contain dispersion to the absorbance (this test solution is surveyed the oil sample preparation with wish) of two kinds of light waves (being selected from about 300 to 1000 millimicrons of wavelength scopes) and utilizes known asphalt content and to the relation between the absorbance of two kinds of light waves, try to achieve the asphalt content of oil sample from measured value. According to the present invention, the instrument that is used for measuring the asphalt content in the heavy hydrocarbon oil also is provided, this instrument comprises checking dipping detector or the flow cell of the test solution of the asphalitine particle that contains dispersion, this test solution is surveyed the oil sample preparation with wish, described dipping detector or flow cell are installed facing to test solution, and can move with stroke up and down, make its contact or leave test solution; A two-wavelength absorption photometric detector, comprise a light source, can allow light see through the session that imports the test solution that floods the given thickness detector or the flow cell from light source, two each can make the interferometric filter that the wave-length coverage that sees through test solution sees through by 300 to 1000 millimicrons different wave length and the light electric transducer that each can be converted to electric current with incident light and the transmitted intensity of two kinds of different wave lengths; And (electronics) computer that current value can be converted to bitumen content. This kind instrument can also comprise control dipping detector or flow cell, two-the wavelength extinction The device of degree detector and computer is in order to successfully carry out the mensuration of multiple test solution.
The basic fundamental of assay method of the present invention is as follows. Take by weighing the oil sample of an amount of (G), and add the solvent of ormal weight, stir subsequently. Then, solution is placed under the rated condition of description, makes the particle size distribution of the asphalitine particle that is settled out as far as possible narrow, so that preparation contains the bitum test solution of dispersion. Make light transmission solution, and the optical density of sample (hereinafter referred to as absorbance (S)) refers to the optical density to two kinds of Different lightwaves in 300 to 1000 millimicrons of scopes. The above-mentioned absorption spectrum of test solution in about 300 to 1000 millimicrons of wavelength scopes that contains the asphalitine particle of dispersion do not have its maximum, and demonstrates a kind of along with the elongated and substantial linear downward trend of wavelength. Fig. 1 illustrates the principle of assay method of the present invention, and among the figure, abscissa represents light wavelength (millimicron) and ordinate represents absorbance. Among Fig. 1, solid line is that test solution is removed the absorption spectrum before the asphalitine, and the absorption spectrum after dotted line to be test solution the remove asphalitine.
Because the asphalitine particle is that the transmission peak wavelength scope is not about 300 to 1000 millimicrons light basically; and absorbance is corresponding with asphalt content; so for example filter with any method, the absorbance of removing the test solution of asphalitine particle is lower than removes the front test solution of asphalitine. More particularly, confirmed by the research work to various heavy hydrocarbon oil, even the kind of oil plant or asphalt content have changed, but do not eliminated the test solution of deasphalting matter particle to λ at (ⅰ)2The absorbance K of light wave4' and to light wave λ1Absorbance K3Difference to K3The i.e. (K of ratio4-K
3）×100/K
3(hereinafter referred to as increment rate) and (ⅱ) remove test solution behind the asphalitine particle to light wave λ1Absorbance K1To absorbance K3Ratio, i.e. K1×100/K
3, still exist a kind of single order relation between (hereinafter referred to as blank rate).
Therefore, malthene (soluble material) is to light wave λ1Absorbance K1Can be by measuring the test solution the asphalitine particle has been dispersed in wherein to the absorbance of two kinds of different wave lengths of suitable selection, and will try to achieve in the relational expression of measured value substitution increment rate and blank rate. In addition, the absorbance K of asphalitine particle5Can be by K3And K1Difference try to achieve.
Therefore, in case make a calibration curve, preferably, then at first can obtain corresponding to absorbance K according to calibration curve according to the IP method or by centrifugal separation technology preparation standard bituminous matter according to standard asphalt matter
5Bituminous matter weight (g), try to achieve the asphalt content of oil sample then by following formula (1).
Asphalt content=g * 100/G(Wt%) (1)
Asphalt content also can be by using by absorbance K
3And K
4The calibration curve of making obtains.In this case, this calibration curve is to compare K according to absorbance
4/ K
3With the gram number of test solution medium pitch matter to absorbance K
3Ratio g/k
3Between single order relation draw.The bituminous matter that can adopt above-mentioned same procedure to try to achieve in the test solution restrains number.
Therefore, if in case determined the K of a certain known test solution
4/ K
3Ratio and g/K
3Relation between the ratio is by measuring absorbance K
3And K
4, and try to achieve bitum weight in grams number from the calibration curve of previous preparation, and calculate asphalt content by formula (1), can carry out bituminous matter simply, effectively and measure.
According to the said determination method, the measured value of the heavy hydrocarbon oil about 0.1 to the 30%(weight of about 50 kinds of asphaltenes) and the related coefficient of IP and the contrast of UOP value are more than 0.99 or 0.99, in addition, variation factor is 5% or less than 5%, be 10% with variation factor or compare that this determination method has shown the degree of accuracy of extremely good analysis less than 10% IP method.Analyze required time each time and be about 40 minutes.Yet, because multiple sample can all be analyzed simultaneously, to compare with habitual rapid test method, each sample has shortened essential analysis time widely.For example, when ten kinds of samples were analyzed simultaneously, each sample required time the longest was 10 minutes.
To narrate the best that realizes the present invention below implements.
When the test solution that the preparation desire is analyzed,, can make the bituminous matter solids precipitation that is present in the oil sample become the fine grained of narrow and small distribution by the designation method of description.The grain size and the distribution thereof of the bituminous matter particle of precipitation have very big influence for the measurement range of the asphalt content in two-wavelength extinction measurement subsequently and the degree of accuracy of mensuration.In order to prevent the bituminous matter solids precipitation in the solution, keep the homogeneously dispersed state of test solution, in whole measuring process, should ceaselessly stir test solution.By optical fiber the light of light source is imported test solution as incident light, see through the solution of specific thickness then.At about 300 to 1000 millimicrons, and preferably in about 500 to 1000 millimicrons of wavelength scopes, measure the absorbance of test solution to two kinds of different light waves.
Utilize light-electric transducer, two kinds of transmission light intensities that will have different wave length all are converted to current value, then in the robot calculator with its input tool designated program, thereby print asphalt content in the oil sample.
Can adopt dipping detection system or flow cell system to finish above-mentioned pair-wavelength absorbance measurement.In last system, the dipping detector of the rear end being furnished with an opening and a reverberator is immersed in the test solution, and incident light and transmitted light then import by the optical fiber that is contained in the detector.In one system of back, by suction test solution is imported flow cell and use the optical fiber that is fixed on face-to-face two sides of flow cell to guide incident light and transmitted light.In both cases, as long as in advance various test solution all is equipped with, just can measure the asphalt content of oil sample effectively in a continuous manner.Yet should be noted that and after measuring each time, need clean dipping detector or flow cell with cleaning solvent, to remove any residual test solution attached thereto.
Aforesaid operations can be saved the labour in a large number with the control of (electronics) computer program.
Can comprise by the method for sample preparation that the present invention analyzes, oil sample that will an amount of (for example 0.3～5.0 gram) be placed on the indication volume (as, 100 milliliters) beaker in, add in a small amount toward beaker is interior again (as, 0.3～5.0 milliliters, be preferably 1.0 milliliters) aromatic hydrocarbon solvent (as, toluene) dissolve it, then, under agitation, with ormal weight (as, 100 milliliters) aliphatic hydrocarbon solvent (as normal heptane) be added to and make asphaltene precipitation in the solution, tolerant cooling at room temperature preferably at 15 to 30 ℃, was cooled off about 30 minutes within then allowing in the beaker.The aliphatic hydrocarbon solvent of above-mentioned use is allowed to warm to about 40 to 90 ℃, is preferably 80 ℃.
Available aromatic hydrocarbon solvent comprises benzene, toluene and dimethylbenzene.Available aliphatic hydrocarbon solvent comprises the aliphatic hydrocrbon of 5 to 12 carbon atoms of tool, for example pentane, hexane, heptane, octane etc.
Prevent that in order to use the trend that precipitates from guaranteeing the dispersion stabilization of bituminous matter particle, this test solution can further contain surfactant, machine oil spreading agent etc.
Adopt the above-mentioned method for preparing test solution, can form the narrow and small bituminous matter particle that is distributed between about 1 micron and about 3 microns, it can bring very big influence to widening the asphaltene concentration scope that can measure and the degree of accuracy that is increased in two-wavelength absorbance detection subsequently.
The test solution that will be dispersed in wherein by the bituminous matter particle that this method is made carries out absorbance measurement, and stir with magnetic stirrer or similar stirrer simultaneously, the distance of two wavelength is minimum to be about 50 millimicrons, be preferably about 50～150 millimicrons, for example, analytical wavelengths is 800 millimicrons, and the contrast wavelength is 675 millimicrons.If the distance between this two wavelength is less than about 50 millimicrons, the degree of accuracy variation of Ce Dinging then.
Consult Fig. 1, suppose that test solution is 800 millimicrons of (K to analytical wavelengths
3) and 675 millimicrons of (K of contrast wavelength
4) absorbance be respectively 1.10 and 1.98, then according to formula (K
4-K
3) * 100/K
3Can draw increment rate is 80.0.According to the relational expression between increment rate and the blank rate, can be 29.1 in the hope of blank rate.Draw K subsequently
1(after removing bituminous matter, viscid bitumen is to the absorbance of 800 millimicrons of light waves)=0.32.So, K
3-K
1(bitum absorbance)=K
5=0.78.According to absorbance K
5Can obtain bituminous matter weight with the calibration curve of bituminous matter weight g.Can be by this gravimetric value in the hope of the asphalt content of oil sample.
Following table 1 is listed with dipping detection system of the present invention and is measured bitum result, and compares with numerical value that known habitual assay method records.As can be seen from Table 1, with method of the present invention and instrument, might measure the asphalt content of wide region with the analytical precision of height.
Table 1
Asphalt content with repeatability of the present invention
Method records degree of accuracy * and calculates gained by (A) conversion gained
The bituminous matter of oil sample (%) IP-method UOP-method IP-method UOP-method
Content (A)
（wt%）
China comforts
Along oil shale fuel 1.2 3.60 0.79 1.0 0.78 1.0
Reduced fuel oil * * 5.5 1.31 3.8 4.7 3.7 4.8
Iran's heavy
Short boiling range slag
Oil 12.8 4.80 8.8 10.9 9.1 10.6
Arabic heavy
The short boiling range of matter
Residual oil 17.9 4.75 12.3 15.3 13.1 15.7
The husky oil of oil
(bursting by freezing) 24.5 4.67 16.8 20.9 16.0 21.3
Hot tearing carburetion 29.5 2.65 20.2 25.0 21.4 25.9
Annotate: *: variation factor
*: viscosity: in the time of 50 ℃, more than viscosity 50 centistokes
The listed measured value of table 1 is to utilize K
4/ K
3And g/K
3Between relation, according to second computing method calculate and.Under this concrete situation, constitute following formula:
Asphalt content (weight %)=0.0287 * (2.43K
3-K
4) * 100/G
Calculate the variation factor of 6 measured values in the table 1 by following formula:
Variation factor (%)=(standard error of representing with the square root of unbiased variance) * 100/ mean value.
When adopting the used identical test solution of flow cell system measurement of the present invention such as table 1, come to the same thing shown in the basic and table 1 of its result.
Hereinafter will illustrate and carry out bituminous matter of the present invention used instrument when measuring.
I dipping detection system:
When the container that magnetic stirrer and test solution will be housed takes predetermined being about to test solution and flooding the position that place on the detector face opposite to, when (promptly locating), make the magnetic stirrer rotation to stir test solution, meanwhile, detector and/or container are risen or fall, thereby make the end of detector, promptly measurement component is dipped into a certain degree of depth essential and that be enough to carry out absorbance measurement in test solution.
In the dipping detector fibre bundle is housed, can guides incident light and transmitted light respectively.Pass the interference filter of the transmitted light of test solution by two different wave lengths, these two optical filters are contained in the fibre bundle exit of guiding transmitted light side by side, and the mensuration of the optical density (absorbance) of test solution is dropped in two about 300 to 1000 millimicrons different wavelength range.
Light-electric transducer utilization such as photoelectric tube, the photoelectric cell, with the intensity-conversion of passing the transmitted light of each optical filter is electric current, and the current value of being changed is imported in the robot calculator of tool designated program, make its operation, print the asphalt content in the oil sample.
When bituminous matter mensuration finishes, under the instruction of robot calculator, detector will be flooded and container is separated from each other, same under the instruction of robot calculator, open the solenoid valve of wash mill, spray to detector thereby make, so that will all rinse out attached to the test solution of detector measurement parts from the cleaning solvent of wash mill input.The cleaning solvent introducing is equipped with in the container of the test solution of having analyzed.After the thorough washing of detector, close solenoid valve, stop washing, and container is removed from locating, simultaneously, the container that another kind of test solution will be housed successively is placed on and locates.By these programs, promptly finish a round-robin bituminous matter and measure.
Fig. 2 and 3 shows the instrumentation diagram that can be used to flood detection system bituminous matter mensuration.Fig. 3 is the enlarged drawing of Fig. 2 critical piece.In these figure, dual wavelength absorption photometric detector 1 is by comprising for example tungsten lamp of light source 2(), interference filter 3(as, 675 and 800 millimicrons), the luminosity parts of photoelectric tube (or solar cell) 4 and amplifier 5 and be contained in that components of assays (promptly flooding detector) on the lifter 6 formed, these two kinds of parts by the guiding incident light fibre bundle 8 and the fibre bundle 9 of guiding transmitted light that only be connected to each other.About the details of photometering parts, can be referring to Fig. 3.Dipping detector 7 has an opening (for example 3 millimeters high, eight mm wides), and there is a reverberator 10 lower end, and clamps (see figure 2) with the anchor clamps 11 of lifter 6.During measurement, detector 7 descends and immerses in the test solution, and when washing and rotating table 12, detector 7 is raised up to the position of leaving test solution on the support.
Consult Fig. 2, the nozzle 13 of washing dipping detector is housed on the lifter 6, these nozzles circularize round detector row, and are connected to the cleaning solvent container 16 that micro-compressor 14 and solenoid valve 15 are housed via polyfluortetraethylene pipe.Lifter is fixed to for example has turntable 12(on locating, put 12 beakers) and the automatic sample conveying device 17 of a magnetic stirrer on.The starting and stop of lifter 6, micro-compressor 14 and turntable 12, and the open and close of solenoid valve 15 are all controlled by the instruction of microcomputer 18.With the electric current output input microcomputer of dual wavelength absorption photometric detector 1, it is asphalt content that this robot calculator is about to this current conversion, and then gets with printer 19.
More particularly, under the signal of microcomputer, the magnetic stirrer of automatic sample conveying device begins rotation, stirs the test solution that is placed in the beaker that locates.Meanwhile, lifter 6 startings allow detector anchor clamps 11 descend, and the opening of detector can be immersed in the test solution.The optical fiber 8 that the light of light source 2 emissions of dual wavelength absorption photometric detector 1 passes the guiding incident light arrives the dipping detector, and penetrates test solution from opening.Part light is absorbed another part light by test solution and then is reflected to reverberator 10.This reflected light is absorbed by test solution once more and arrives interference filters 3 by the fibre bundle 9 that guides transmitted light, at this moment, select the transmitted ray of two wavelength by two interference filters 3, and then every bundle transmitted light is converted to electric current by corresponding photoelectric tube 4, amplify through corresponding amplifier 5, import then in the microcomputer 18.
In microcomputer 18, the electric current input is converted to transmission coefficient t (transmitted light I and incident light I
oRatio, i.e. I/I
o), and then T is converted to absorbance K(log
10L/T).Increment rate-blank the rate and the absorbance difference K that the absorbance of gained are used for having imported in advance computing machine
3-K
1To the proportionate relationship of the calibration curve of asphalt content,, import printer 19 then to calculate asphalt content.Simultaneously, relation between the asphalt content that asphalt content that the asphalt content that asphalt content that application the present invention of input in advance records and IP method record and the present invention record and UOP method record is converted to IP asphalt content and UOP asphalt content with resulting asphalt content.After input finished, microcomputer 18 sent signal starting micro-compressor 14, makes in the container 16 and presses liter.Then, lifter 6 begins to move, and when detector anchor clamps 11 rose, solenoid valve 15 was opened at once, allows cleaning solvent (as normal heptane) from nozzle 13 ejections, cleans dipping detector 7.
Afterwards, the turntable 12 of automatic sample conveying device 17 begins to rotate again, makes next desire analyze test solution and is positioned at the position of mensuration, and repeat above-mentioned same operation automatically.
Not easy-to-use when the nozzle ejection solvent washs when the sample of measuring, can on turntable 12, alternately use the beaker of containing test solution and the beaker of containing cleaning solvent (as toluene) instead and guarantee the effect of washing.
II flow cell system:
Flow cell system and device (replacing flooding detector) with flow cell, can operate the identical method of above-mentioned dipping detection system device operates, but, guide the end of the fibre bundle of incident light and transmitted light then to be fixed on the both sides in transparent flow pond respectively, it is being faced one another, and, replace used wash mill in the dipping detection system with aspirator, the test solution of analyzing is extracted out.
According to the flow cell system, when the suction pipe end of linking flow cell was immersed in the test solution, vacuum pump was about in the test solution suction suction pipe and it is flowed in flow cell.When liquid stream flows through, measure the absorbance of test solution between the two ends of the fibre bundle that guides incident light and transmitted light respectively.Then test solution is drawn in the airtight waste reservoir.Bleeding with vacuum pump makes waste reservoir decompression, so that make the test solution of back suck suction pipe to give fixed flow velocity.In order to prevent that waste liquid and waste gas from polluted pump, bleed when reducing pressure through a cold-trap device.After measuring each time, any attached to the residual test solution on the walls such as suction pipe, flow cell, can come in addition eccysis with the method that the container that fills cleaning solvent replaces the beaker that fills test solution.Therefore, this flow cell system does not need to flood needed independently wash mill in the detection system.
Fig. 4 is a flow cell system and device synoptic diagram of measuring asphalt content.When microcomputer 18 sends signal, lifter 6 startings, and flow cell 20(that flow cell anchor clamps 21 are clamped such as thickness are 3 millimeters glass container) descend at once, up to the suction pipe 22(that is connected to flow cell 20 lower ends as,, a polyfluortetraethylene pipe, internal diameter is 2 millimeters) end when just inserting the test solution that is stirred by magnetic stirrer, this magnetic stirrer is to be contained on the measuring position of automatic sample conveying device 17.Start vacuum pump 23 suction test solutions then, and utilize pressure control valve 24 adjustment of suitably reduce pressure, make test solution mobile by certain flow velocity (preferably about 10～30 ml/min).When test solution flows through flow cell 20, with dual wavelength absorption photometric detector 1 measure two kinds of wavelength passing test solution (as, 675nm and 800nm) transmitted light, and be current value with the intensity-conversion of the transmitted light that records.Current output value input microcomputer 18 with gained with they (current output value), is converted to absorbance again.Preferably after vacuum pump 23 starts about 20 seconds, just current value is imported in the microcomputer 18.
When a mensuration process finished, lifter 6 rose, and suction pipe 22 is lifted, and after the several seconds, stops vacuum pump 23.Preferably about 60 seconds of the driving time of vacuum pump.And then starting automatic sample conveying device 17, turntable 12 is rotated, and make the beaker that fills cleaning solvent (as toluene) be positioned at the position of measurement, use vacuum pump 23 suction solvent subsequently, to reach purpose with the inwall cleaning of suction pipe 22 and flow cell 20.After washing finished, turntable 12 rotated again, next sample is taken to the position of measurement.
Above-mentioned sequence of operations is controlled by the microcomputer 18 of program design entirely.The result that bituminous matter is measured is got according to the instruction of being defeated by robot calculator 18 by printer 19 continuously.
Test solution of having analyzed and cleaning solvent all are collected in the waste reservoir 25.In order to prevent to pollute vacuum pump 23, be preferably between reservoir 25 and the pump 23 cold-trap device 26 is set.
Among Fig. 4, fixedly the flow cell anchor clamps 21 of flow cell 20 and dual wavelength absorption photometric detector 1 are all linked lifter 6.Flow cell 20 and its anchor clamps 21 can be assemblied on any position of pipeline (test solution of suction pipe 22 conveyings circulates in this pipeline), might not need to be fixed on the lifter 6.Dual wavelength absorption photometric detector 1 also not necessarily will be fixed on the lifter 6.Necessary is that move with the upper and lower stroke of lifter the end of suction pipe 22, makes it can be immersed in the test solution and rise.Therefore, when flow cell anchor clamps 21 are not to be fixed under the situation of lifter 6, suction pipe 22 can be fixed to the position of close suction pipe end on the lifter 6.
As mentioned above, the present invention eliminated with the method for the asphalt content in the habitual mensuration heavy hydrocarbon oil related shortcoming, narrow such as minute, complicated operations, needed labour, measurement range that every part of sample is required, degree of accuracy can not be satisfactory or the like in some cases.In other words, the present invention might automatically carry out the bituminous matter of many kinds of samples and measure, and shorten the minute of each sample with the degree of accuracy of height, does not need more labour.
After at length having narrated the present invention and having consulted its specific embodiments, obviously, those skilled in the art can carry out various changes and improvements in not breaking away from spirit of the present invention and standard.
Claims (11)
1, measures the method for the asphalt content in the heavy hydrocarbon oil, this method comprises that mensuration bituminous matter particle has been dispersed in the absorbance (this bituminous matter particle from desire survey oil sample preparation) of test solution to being selected from two kinds of light waves in about 500 to 1000 millimicrons of wavelength scopes wherein, and utilize relation between the absorbance of known asphalt content and two kinds of light waves, try to achieve the asphalt content of oil sample from measured value.
2, be by aromatic hydrocarbon being added in the oil sample, they are mixed each other, again aliphatic hydrocrbon is added in the solution, make the bituminous matter solids precipitation according to the test solution that the process of claim 1 wherein, and allow solution cool off to prepare.
3, according to the method for claim 2, wherein described aliphatic hydrocrbon is warmed to about 40 to 90 ℃.
4, according to the method for claim 3, wherein described aliphatic hydrocrbon is warmed to 80 ℃.
5, according to the process of claim 1 wherein selected two kinds of wavelength, be separated by 50 millimicrons at least as absorbance measurement.
6, according to the method for claim 5, wherein the distance between two kinds of wavelength is about 50 to 150 millimicrons.
7, be used for measuring the instrument of heavy hydrocarbon oil medium pitch matter content, this instrument comprises 1) be used for detecting dipping detector or the flow cell that the bituminous matter particle has been dispersed in test solution wherein, this bituminous matter particle is surveyed the oil sample preparation from desire, described dipping detector or flow cell are placed face-to-face with test solution, and can go up, move down, make it can contact or leave test solution with test solution, 2) a kind of pair-wavelength absorption photometric detector, comprise light source, the light transmission that light source is sent imports the session of the test solution of the given thickness in dipping detector or the flow cell, two all can make and to see through test solution, be selected from the interference filter of the different light-wave transmission of about 300 to 1000 millimicrons of wavelength scopes, and can be the light-electric transducer of electric current with the intensity-conversion of the transmitted light of each incident light and two kinds of different wave lengths of tool all, 3) current value can be converted to the robot calculator of asphalt content.
8, according to the instrument of claim 7, wherein, be elected to be two kinds of wavelength of absorbance measurement, be separated by 50 millimicrons at least.
9, instrument according to Claim 8, wherein the distance between two kinds of wavelength is by 50 to 150 millimicrons.
10, according to the instrument of claim 7, wherein dipping detector or flow cell are furnished with wash mill, and be any attached to the residual test solution on dipping detector or the mobile pool wall in order to remove.
11, according to the instrument of claim 7, wherein said instrument also comprises the device of control dipping detector or flow cell, dual wavelength absorption photometric detector and calculation element, so that carry out the mensuration of many kinds of test solutions continuously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87101666 CN1017186B (en) | 1985-11-08 | 1987-02-28 | Rapid determination of asphaltene content and device therefor |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60248733A JPS62110135A (en) | 1985-11-08 | 1985-11-08 | Method and apparatus for quantifying concentration of asphaltene |
| CN 87101666 CN1017186B (en) | 1985-11-08 | 1987-02-28 | Rapid determination of asphaltene content and device therefor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87101666A CN87101666A (en) | 1988-09-07 |
| CN1017186B true CN1017186B (en) | 1992-06-24 |
Family
ID=25742290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87101666 Expired CN1017186B (en) | 1985-11-08 | 1987-02-28 | Rapid determination of asphaltene content and device therefor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1017186B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7394545B2 (en) * | 2005-07-11 | 2008-07-01 | Ge Betz, Inc. | Apparatus for characterizing and measuring the concentration of opaque particles within a fluid sample |
| CA2996950C (en) * | 2015-09-01 | 2023-05-09 | Bp Corporation North America Inc. | Predicting solvent power of light oils |
| CN110487682B (en) * | 2019-08-08 | 2021-09-03 | 生态环境部华南环境科学研究所 | Test tube wrapping paper device |
| CN111650148A (en) * | 2020-06-22 | 2020-09-11 | 中国海洋石油集团有限公司 | Ultraviolet evaluation method for dissolution effect of asphaltene scavenger |
| CN112415180B (en) * | 2020-12-10 | 2021-09-10 | 广西交科集团有限公司 | Method for selecting base asphalt for rubber asphalt based on ash correlation analysis |
-
1987
- 1987-02-28 CN CN 87101666 patent/CN1017186B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87101666A (en) | 1988-09-07 |
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