CN103645171B - A kind of method detecting waste oil based on Raman spectroscopy - Google Patents
A kind of method detecting waste oil based on Raman spectroscopy Download PDFInfo
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- CN103645171B CN103645171B CN201310643090.1A CN201310643090A CN103645171B CN 103645171 B CN103645171 B CN 103645171B CN 201310643090 A CN201310643090 A CN 201310643090A CN 103645171 B CN103645171 B CN 103645171B
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Abstract
The invention discloses a kind of method detecting waste oil based on Raman spectroscopy, it comprises following detecting step: adopt the incident laser light source of 532nm wavelength to carry out Raman spectroscopy scans to refining waste oil, obtain the Raman spectrogram of refining waste oil, determine the Characteristic Raman peak of refining waste oil; Wherein, described Characteristic Raman peak is positioned at the interval 1800cm of Raman frequency shift
-1-2200cm
-1, its peak curve is level and smooth bag-like and the half-peak breadth at described Characteristic Raman peak has exceeded the interval 3500cm of Raman frequency shift
-1-50cm
-1; The incident laser light source of 532nm wavelength is adopted to carry out Raman spectroscopy scans to oil sample to be measured, obtain the Raman spectrogram of oil sample to be measured, the Raman spectrogram of the Raman spectrogram of described oil sample to be measured and described refining waste oil is contrasted, when there is described Characteristic Raman peak, judge that described oil sample to be measured contains waste oil.Above-mentioned detection method is convenient and swift and reliable and practical.
Description
Technical field
The invention belongs to edible oil quality analysis technical field, particularly a kind of method detecting waste oil based on Raman spectroscopy.
Background technology
From 2009, a series of " waste oil " case that China cracks discloses China not only to be existed really, and has defined Dark Industry Link and the network that " edible oil " is made and sold in utilization " waste oil ".By these Dark Industry Links and network, " waste oil " of enormous amount has extensively come into the market and the dining table that refluxes.In view of harmfulness and the seriousness of sort of activity, it is " waste oil " criminal offence that juridical authorities of China will utilize " waste oil " to make and sell " edible oil " formally qualitative specially, is suitable for determining a crime " mixing poisonous, harmful non-food raw material in the food of producing and selling " of penal provision.
" waste oil ", formal name used at school recycled wood materials, it is the general name of the waste grease of separation and recovery from changing food waste, waste grease, all kinds of SDS in broiler chickens processing waste, comprise: (1) meal kitchen waste grease, refers to the waste grease of separation and recovery the rubbish and emission produced from catering trade places such as hotel, restaurant, dining rooms; (2) fry waste grease, refer to the waste grease through high temperature fried food repeatedly; (3) animal waste grease, refers to the grease extracted with all kinds of SDS in broiler chickens processing waste (comprising meat, internal organ, skin) processing.In China, no matter be from absolute magnitude, or ubiquity, meal kitchen waste grease is all " waste oil " main and fixing source undoubtedly.What is more important, meal kitchen waste grease is that current criminal gang is for making and selling the raw material that " edible oil " is the most frequently used and be easy to get most.
The Main Patterns that " waste oil " criminal gang utilizes " waste oil " to make and sell " edible oil " is: a large amount of purchase meal kitchens waste grease is as feedstock oil, be separated through heating and filtering and obtain " waste oil " crude oil, crude oil makes refining " waste oil " (also can unite and be grouped into waste oil) through deodorization, depickling, decolouring.These refining waste oils because be difficult to effectively make a distinction with edible oil, so sold to edible oil processing enterprise in batches, or mix in edible vegetable oil and sell to edible oil market and pharmacy corporation.
In recent years, the sanitation Ministry tissue whole nation expert of association area, scholar and technician have carried out the research cooperation research of large-scale " waste oil " detection technique, successively " waste oil " detection method of collection and checking reaches kind more than 350, but still fails so far to find the reliable method of inspection be suitable for.Such as, there is the correlation technique adopting Raman spectroscopy to detect waste oil at present, but because all therefrom do not find the mark that effectively can be different from waste oil and edible oil, so the control of whole testing process complicated difficult, testing result is also inaccurate.And in prior art, for reducing background, do not shield small peak, and make structure of matter analysis more accurate, generally carry out Raman spectroscopy scans with the incident light source of 780nm wavelength, but " waste oil " that scan out thus does not morphologically have differentiable significant difference with the Raman spectrum of edible vegetable oil, cause those skilled in the art cannot obtain being different from by the graphs of both contrasts the Raman peaks of normal oil, so generally believe and only effectively can not detect waste oil by Raman spectroscopy, specifically can see Figure of description 1 and 2, the Raman spectrogram of i.e. refining " waste oil " DJ013 and soybean product oil ZC003 (wherein, DJ013 and ZC003 is sample number into spectrum, can see " the food plant product oil information " form in instructions embodiment content).Therefore, Raman spectroscopy can carry out in conjunction with other detection method usually together, but its complicated operation and still do not form reliable detection system.As further improvement, someone is for whole Raman collection of illustrative plates, the raman scattering intensity contrast of waste oil and edible oil is studied as point of penetration, characteristic fingerprint pattern detection method is proposed, but it still fails to find waste oil to be obviously different from the feature of edible oil, and complex operation step, completing of each step needs to draw through conclusion or summary by analyzing Raman curve, cause error constantly to expand like this, the accuracy of testing result can not be ensured.
Therefore, this technical barrier unassailable reason of a specified duration is detected for " waste oil ", the more consistent view of brainstrust is: through refining with blend two links, the proterties of " waste oil " is very close with normal edible vegetable oil, therefore is difficult to find the general and applicable mark of qualification " waste oil " or this mark not to exist.
Summary of the invention
The object of the present invention is to provide a kind of method detecting waste oil based on Raman spectroscopy, the method is intended to be difficult to successfully effectively detect waste oil in solution prior art, and makes the technical matters that waste oil and normal edible oil make a distinction.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
Detect a method for waste oil based on Raman spectroscopy, it comprises following detecting step:
Adopt the incident laser light source of 532nm wavelength to carry out Raman spectroscopy scans to refining waste oil, obtain the Raman spectrogram of refining waste oil, determine the Characteristic Raman peak of described refining waste oil; Wherein, described Characteristic Raman peak is positioned at the interval 1800cm of Raman frequency shift
-1-2200cm
-1, its peak curve is level and smooth bag-like, and the half-peak breadth at described Characteristic Raman peak has exceeded the interval 3500cm of Raman frequency shift
-1-50cm
-1;
Adopt the incident laser light source of 532nm wavelength to carry out Raman spectroscopy scans to oil sample to be measured, obtain the Raman spectrogram of oil sample to be measured; The Raman spectrogram of the Raman spectrogram of described oil sample to be measured and described refining waste oil is contrasted, when described Characteristic Raman peak appears in described oil sample to be measured, judges that described oil sample to be measured contains waste oil.
Above-mentioned detection method is different from the composition of edible oil as point of penetration using searching from refining waste oil, and found by Raman spectroscopy scans, waste oil exists the improper composition that some are different from edible oil.See Fig. 3, under the energy excitation of the incident laser light source of wavelength 532nm, can at scanning wave band 3500cm after these improper compositions are stimulated
-1~ 50cm
-1in, only there is a huge level and smooth bag-like Raman peaks.This bag-like Raman peaks has great width, and its half-peak breadth has reached or even exceeded above-mentioned whole scanning wave band, and the position at peak is at the interval 2200cm of Raman frequency shift
-1~ 1800cm
-1.Through a large amount of experimental verifications, this bag-like Raman peaks only appears in the oils containing " waste oil ", do not appear in normal edible oil, therefore, by the confirmation at this Characteristic Raman peak, those skilled in the art only need carry out by suitable incident light source the judgement that Raman spectroscopy scans can carry out waste oil, and operation is simple and reliable, is easy to distinguish.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the Raman spectrum of the refining waste oil formed under the incident light source scanning of 780nm wavelength;
Fig. 2 is the Raman spectrum of the soybean product oil formed under the incident light source scanning of 780nm wavelength;
Fig. 3 is the Raman spectrum of the refining waste oil formed under the incident light source scanning of 532nm wavelength;
Fig. 4 is the Raman spectrum of the soybean product oil formed under the incident light source scanning of 532nm wavelength;
Fig. 5 is stacking diagram's (full scale) of Fig. 3 and Fig. 1 Raman spectrum;
Fig. 6 is stacking diagram's (full scale) of Fig. 2 and Fig. 4 Raman spectrum;
Fig. 7 is the infrared spectrogram of refining waste oil;
Fig. 8 is the infrared spectrogram of soybean product oil;
Fig. 9 is the Raman spectrogram (full scale) of 40 parts of meal kitchen waste greases;
Figure 10 is the Raman spectrogram (full scale) of 24 parts of frying waste greases;
Figure 11 is the Raman spectrogram (full scale) of 3 parts of animal waste greases;
Figure 12 is the Raman spectrogram (same to scale) comprising Fig. 9-11 three kinds of raw oil materials;
Figure 13 is the Raman spectrogram of a meal kitchen waste grease sample at different refining stage;
Figure 14 is the Raman spectrogram of another meal kitchen waste grease sample at different refining stage;
Figure 15 is the Raman spectrogram of an edible blend oil at different heating temperature;
Figure 16 is the Raman spectrogram of a peanut oil at different heating temperature;
Figure 17 is the Raman spectrum (same to scale) of 38 kinds of refining trench oil samples;
Figure 18 is the Raman spectrum (full scale) of 38 kinds of refining trench oil samples;
Figure 19 is the Raman spectrum (same to scale) of 7 parts of soy bean oils;
Figure 20 is the Raman spectrum (same to scale) of 8 parts of soybean product oils;
Figure 21 is the Raman spectrum (same to scale) of 5 parts of vegetable seed crude oil;
Figure 22 is the Raman spectrum (same to scale) of 6 parts of tea seed product oils;
Figure 23 is the Raman spectrum (same to scale) of 15 parts of edible blend oils;
Figure 24 is the Raman spectrum (same to scale) of 7 parts of olive product oils;
Figure 25 is the Raman spectrum (same to scale) of 36 portions of peanut oil;
Figure 26 is the Raman spectrum (same to scale) of 5 parts of mustard seed product oils;
Figure 27 is the Raman spectrum (same to scale) of 8 parts of palm crude oil;
Figure 28 is the Raman spectrum (same to scale) of 13 parts of refined palm oil;
Figure 29 is the Raman spectrum (same to scale) of 4 parts of sunflower seeds crude oil;
Figure 30 is the Raman spectrum (same to scale) of 6 parts of sunflower seeds product oils;
Figure 31 is the Raman spectrum (same to scale) of 5 parts of crude maize oil;
Figure 32 is the Raman spectrum (same to scale) of 8 parts of corn product oils;
Figure 33 is the Raman spectrum (same to scale) of 2 parts of Chinese prickly ash product oils;
Figure 34 is the Raman spectrum (same to scale) of 2 parts of refined coconut oil;
Figure 35 is the Raman spectrum (same to scale) of 1 part of rice bran crude oil;
Figure 36 is the Raman spectrum (same to scale) of 1 part of cottonseed crude oil;
Figure 37 is the Raman spectrum (same to scale) of 1 part of linseed product oil;
Figure 38 is the Raman spectrum (same to scale) of 11 parts of sesame oil;
Figure 39 is the Raman spectrum (full scale) of 11 parts of sesame oil;
Figure 40 is the morphologic change (full scale) that refining waste oil blends soy bean oil Raman spectrum;
Figure 41 is intensity change (same to scale) that refining waste oil blends soy bean oil Raman spectrum;
Figure 42 is the morphologic change (full scale) that refining waste oil blends crude maize oil Raman spectrum;
Figure 43 is intensity change (same to scale) that refining waste oil blends crude maize oil Raman spectrum;
Figure 44 is the morphologic change (full scale) that refining waste oil blends rice bran crude oil Raman spectrum;
Figure 45 is intensity change (same to scale) that refining waste oil blends rice bran crude oil Raman spectrum;
Figure 46 is the morphologic change (full scale) that refining waste oil blends cottonseed crude oil Raman spectrum;
Figure 47 is intensity change (same to scale) that refining waste oil blends cottonseed crude oil Raman spectrum;
Figure 48 is the morphologic change (full scale) that refining waste oil blends peanut product oil Raman spectrum;
Figure 49 is intensity change (same to scale) that refining waste oil blends peanut product oil Raman spectrum;
Figure 50 is the morphologic change (full scale) that refining waste oil blends rice product oil Raman spectrum;
Figure 51 is intensity change (same to scale) that refining waste oil blends rice product oil Raman spectrum;
Figure 52 is the morphologic change (full scale) that refining waste oil blends corn product oil Raman spectrum;
Figure 53 is intensity change (same to scale) that refining waste oil blends corn product oil Raman spectrum;
Figure 54 is the morphologic change (full scale) that refining waste oil blends olive product oil Raman spectrum;
Figure 55 is intensity change (same to scale) that refining waste oil blends olive product oil Raman spectrum;
Figure 56 is the morphologic change (full scale) that refining waste oil blends soybean product oil Raman spectrum;
Figure 57 is intensity change (same to scale) that refining waste oil blends soybean product oil Raman spectrum;
Figure 58 is the Raman spectrum (same to scale) same edible blend oil being carried out to multiple scanning measurement;
Figure 59 is the Raman spectrum (same to scale) same refining trench oil samples being carried out to scanning survey;
Figure 60 is the Raman spectrum (same to scale) same edible blend oil being carried out to repetitive operation measurement;
Figure 61 is the Raman spectrum (same to scale) same refining trench oil samples being carried out to repetitive operation measurement;
Wherein, Fig. 7-Figure 61 is formed under the incident light source scanning of 532nm wavelength; The scanning Raman frequency shift interval of Fig. 1-Figure 61 is 4000cm
-1~ 50cm
-1between, with the contrast of scale mainly raman scattering intensity, full scale is mainly the contrast of Raman peaks form, and in Fig. 1-Figure 61, except Fig. 7-8, the horizontal ordinate of other figure is Raman shift (cm
-1), ordinate is the horizontal ordinate of raman scattering intensity (cps), Fig. 7-8 is wave number (cm
-1), ordinate is transmitance (%).
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Based on the finiteness of the incident light source of existing Raman spectroscopy scans apparatus preparation, the incident laser light source of what those skilled in the art generally can select is 780nm and 532nm wavelength, and through long-term practical experience, those skilled in the art know, Raman scanning about oil component is all carry out under the light source of 780nm wavelength, because the composition of edible oil can be excited under the LASER Light Source of 780nm wavelength, and compared to the wavelength light source of 532nm, background can be avoided under such wavelength too large, be easy to observe out peak situation to be effectively specified to separation structure.But the applicant changes conventional analysis of the molecular structure thinking, never go out peak position to start with, the light source utilizing energy higher scans, as 532nm, excite the composition that cannot excite under 780nm wavelength light source, find the Characteristic Raman peak that obviously can be different from edible oil.
Based on above-mentioned theory, the embodiment of the present invention provides a kind of method detecting waste oil based on Raman spectroscopy, and the method comprises following detecting step:
The incident laser light source of S01, employing 532nm wavelength carries out Raman spectroscopy scans to refining waste oil, obtains the Raman spectrogram of refining waste oil, determines the Characteristic Raman peak of described refining waste oil; Wherein, described Characteristic Raman peak is positioned at the interval 1800cm of Raman frequency shift
-1-2200cm
-1, its peak curve is level and smooth bag-like, and the half-peak breadth at described Characteristic Raman peak has exceeded the interval 3500cm of Raman frequency shift
-1-50cm
-1;
The incident laser light source of S02, employing 532nm wavelength carries out Raman spectroscopy scans to oil sample to be measured, obtains the Raman spectrogram of oil sample to be measured; The Raman spectrogram of the Raman spectrogram of described oil sample to be measured and described refining waste oil is contrasted, when described Characteristic Raman peak appears in described oil sample to be measured, judges that described oil sample to be measured contains waste oil.
Particularly, in above-mentioned steps S01, waste oil is the waste oil of existing common cognition, comprises refining waste oil, and it is generally obtained through deodorization, depickling, decolouring by waste oil crude oil.Refining waste oil and edible oil are easy to obscure, be difficult to distinguish so that come into the market in a large number, pretend to be or mix edible oil, therefore, refining waste oil be described detection method mainly for object.Described refining waste oil is formed by the refining of waste oil crude oil, waste oil crude oil is preferably at least one in meal kitchen waste grease, frying waste grease, animal waste grease, more effective detection can be obtained like this, and this is commonplace common waste oil, ensure that the practicality of this detection method.
In above-mentioned steps S02, described oil sample to be measured comprises edible vegetable oil, described edible vegetable oil is soy bean oil and product oil thereof, vegetable seed crude oil, tea-seed oil, edible blend oil, olive product oil, peanut oil, sesame oil, mustard seed product oil, palm crude oil, refined palm oil, sunflower seeds crude oil and product oil thereof, crude maize oil and product oil thereof, refined coconut oil, rice bran crude oil, cottonseed crude oil, rice product oil, refining safflower oil, linseed product oil, during at least one in Chinese prickly ash product oil, described Characteristic Raman summit is more given prominence to and is easily distinguished, thus more accurately and effectively edible vegetable oil and waste oil are made a distinction, certainly these edible vegetable oils are all representative, show also described detection method and there is universality.
The applicant finds, above-mentioned Characteristic Raman peak needs enough excitation energies to produce, and when incident light source wavelength is 532nm, scanning waste oil can form the obvious Characteristic Raman peak of above-mentioned feature.Therefore, if when adjustment incident light source wavelength is to 532nm, also do not find described Characteristic Raman peak, then can judge that oil sample to be measured is not waste oil or at least can think that the percent by volume of waste oil to vide infra elaboration lower than 10%(), make detection have practical value and handled easily like this.Along with the progress of technology, perhaps there will be more light source and select, we can therefrom select suitable incident light source, and choice criteria can occur that above-mentioned Characteristic Raman peak is as the criterion.
Based on the acquisition at above-mentioned Characteristic Raman peak, the effective detection of blending oil containing waste oil is also become a reality, wherein, blend oil and be preferably the edible vegetable oil containing waste oil.When blend in oil containing percent by volume be the waste oil of 10% time, the form at Characteristic Raman peak just presents substantially, along with the increase of the incorporation of refining waste oil, the Raman spectrum form of blending oil sample is more similar to the Characteristic Raman peak of refining " waste oil ", and the intensity of Raman peaks is also with the trend that mixed ratio increases in gradient.When trench oil content lower than 10% time, also there will be this Characteristic Raman peak, just intensity is relatively weak, higher to the accuracy requirement of detecting instrument.
In practice, we by the accurate contrast of the Raman spectrum of waste oil and edible vegetable oil, can obtain testing result accurately.In order to more precisely effectively carry out the contrast between the glossy spectrum of refining trench and oil sample spectrum to be measured, preferably, oil sample to be measured is being carried out in the step of Raman spectroscopy scans, repeatedly scanning can be sampled to oil sample to be measured, and each scanning curve is placed in same Raman spectrogram, the Raman spectrogram (such as Figure 58) of the oil sample described to be measured formed after obtained each sample curve combining, or in the step at Characteristic Raman peak determining waste oil, sampling scanning can be carried out by the various refining waste oils different to raw materials, and each sample scanning curve is placed in same Raman spectrogram, the Raman spectrogram (such as Figure 18) of the described refining waste oil formed after obtained curve combining.Certainly it is further preferred that the Raman spectrogram of the both rear formation of each sample curve of spectrum superposition, such error that relatively can farthest reduce in testing process, makes testing result more reliable.
Further, for verifying the reliability of testing result better, the raman scattering intensity of further contrast characteristic's Raman peaks on the basis that we can compare above, when the laser energy of Raman scanning is 5.0mW, the intensity of its peak height is more than or equal to 1.0 × 10
5cps.
In above-mentioned steps S01 and S02, described Raman spectroscopy scans can be undertaken by existing Raman spectroscopy scans instrument, to obtain the Raman spectrum of testing sample.
Above-mentioned detection method determines containing the improper composition being different from edible vegetable oil in waste oil, and using these improper compositions under certain excitation energy can morphogenesis characters Raman peaks as examination criteria.By only utilizing the mode of Raman spectroscopy scans can realize successful detections of waste oil in the incident light source and scanning wave-number range of certain wavelength, quick and practicability and effectiveness simple to operate.
Now for specifically a large amount of detection operations and experimental result, the present invention is further elaborated.
1, the preparation of experiment material
1.1 edible vegetable oil
Food plant crude oil 61 parts, comprise soy bean oil, crude maize oil, 10 degree of palm oils, 24 degree of palm oils, 33 degree of palm oils, 52 degree of palm oils, just squeeze rapeseed oil, sunflower seeds crude oil, peanut oil, sesame oil, rice bran oil crude oil, cottonseed crude oil, provided by Nanhai Grease Industrial (Chi Wan) Co., Ltd.;
Food plant product oil 109 parts, comprise the purified soyabean oil of different manufacturers and different brands, refined maize's oil, peanut oil, sesame oil, olive oil, tea-seed oil, maize germ oil, Rice oil, sunflower oil, Canola oil, Zanthoxylum essential oil and blending stock, buy from Ge great supermarket, Shenzhen respectively.
For details, see the appendix one for the sample message of edible vegetable oil.
1.2 recycled wood materials
Meal kitchen waste grease 40 parts, gathers from being engaged in of specifying of the Shenzhen Municipal Government Teng Lang regenerated resources Development Co., Ltd of Shenzhen that changing food waste centrally disposes and Shenzhen Rui Saier Environmental Protection Co.Ltd. respectively;
Frying waste grease 30 parts, from Shenzhen, each eating and drinking establishment gathers respectively;
Animal fat 3 parts, is provided by Nanhai Grease Industrial (Chi Wan) Co., Ltd..
For details, see the appendix two for the sample message of recycled wood materials.
1.3 self-controls refining " waste oil "
For meeting the sampling of various waste oil, according to existing conventional refinery process, different waste oil raw materials is refined.Comprise following step:
(1) feedstock capture and process: on average monthly respectively gather 1 batch of meal kitchen waste grease from Teng Lang company and Rui Saier company respectively.During collection, in the raw material oil sump depositing meal kitchen waste grease, each point gathers oil sample, uses after mixing.
(2) " waste oil " crude oil preparation: get meal kitchen waste grease 2000g in stainless-steel pan, put magnetic agitation hot plate and be under agitation heated to 80-90 DEG C, keep about 1h.After slightly cold, add filtration aid suction filtration with filter paper, collect the grease in filter flask;
(3) " waste oil " deodorization preparation: get above-mentioned grease 1000g in 2000ml tri-mouthfuls of round-bottomed flasks, connect the interface between each vessel, close nitrogen inlet valve, open vacuum pump and system is vacuumized (10mmHg), open the electric jacket power switch under there-necked flask simultaneously, connect condensate water.When oil sample temperature rises to about 150 DEG C, open nitrogen inlet valve, make nitrogen enter reaction bulb and gas stripping is produced to oil, control temperature is at 250-260 DEG C, and air lift distillation 2.5-3h, turns off electric jacket power supply, continue logical nitrogen, and continue to vacuumize system, until oil temperature drops to 40-50 DEG C.Close vacuum pump, continue logical nitrogen until be normal pressure in reaction bulb, close nitrogen, be cooled to about the 80 DEG C greases collected in reaction bulb;
(4) " waste oil " depickling preparation: grease is transferred in 2000ml beaker, add 200ml saturated aqueous common salt, be heated to 60 DEG C together under stirring, stirring rate controls at 80-120rpm, under agitation slowly gradation add 80ml concentration be 20% aqueous slkali carry out saponification and be about 10min.Reaction terminates rear stopping and stirring, constant temperature standing sedimentation 20min at about 60 DEG C, folds filtered through gauze while hot and removes soap blank, collect liquid fat with layer 2-4;
(5) " waste oil " decolouring preparation: grease is transferred in 2000ml tri-mouthfuls of flat bottom flasks, put magnetic agitation hot plate and be under agitation heated to 110 DEG C together, add 2.5% atlapulgite heavy relative to oil and 0.5% activated charcoal, vacuum decoloration 30min at temperature remains on 105-120 DEG C.Carry out vacuum filtration with Buchner funnel, bottle,suction while hot, collect the grease in filter flask.
(6) refining " waste oil " sample survey: the physical and chemical index adopting national standard method inspection each sample, the results are shown in table 1-1 and 1-2.
The assay of table 1-1 refining " waste oil " conventional index
The assay (average, n=13) of table 1-2 refining " waste oil " contamination index
Have employed 38 batches of refinings " waste oil ", for details, see the appendix three for its sample message.
2, detecting instrument
ThermoFisherScientific company of the micro-Raman spectroscopy DXRRamanMicroscope(U.S.), be equipped with the atlas analysis software of 780nm and 532nm LASER Light Source, instrument.
Instrument parameter is as follows:
(1) incident light source: 532nm LASER Light Source or 780nm LASER Light Source.Laser energy 5.0mW.
(2) optical slits is gone out: 25nm.
(3) time shutter: 0.1sec.
(4) exposure frequency: 50.
(5) sweep limit: 4000cm
-1~ 50cm
-1.
3, detection method
Open light source and Raman spectrometer, complete after self-inspection until instrument and start sample measurement.Get oil sample 10 μ L in the microslide central authorities being lined with tinfoil paper, be placed in by microslide on the microscope slide platform of instrument, focus incoming light in sample droplet center, is closed microscope stage upper cover by movable object-carrying stage.Press selected scope and the Raman spectrum of parameter scanning sample, after completing scanning, shift out microslide.
Principle involved by detection method and concept have:
(1) definition of Raman light: Raman light is the specific scattered light of a class.Scattered light is divided into two classes, and a class is elastic scattering light, and another kind of is inelastic scattering light.Elastic scattering light only changes the direction of propagation of light, does not change the frequency of light; Inelastic scattering light had both changed the direction of propagation of light, also changed the frequency of light.Elastic scattering light is called as Rayleigh scattering light, and inelastic scattering light is called as Raman diffused light.It is all the important optical phenomena with the naming of its discoverer.
(2) mechanism of Raman light: the energy of molecule absorption incident photon is excited to high-energy state by ground state, launches photon when molecule returns low-energy state from high-energy state transition.If molecule comes back to ground state from high-energy state, launch photon identical with the energy of incident photon, both frequencies are identical, and the utilizing emitted light produced is Rayleigh scattering light; If molecule gets back to the energy state of an energy higher than ground state from high-energy state, launch the energy of photon lower than incident photon, the former frequency is also less than the latter.The utilizing emitted light produced is Raman diffused light.
(3) relation of Raman light and molecular structure: the energy difference launching photon and incident photon equals the energy difference of molecule itself vibrates energy inter-stage.The structure of molecule is different, the differential difference of its energy of vibration, shows as and produces the different Raman bands of a spectrum of difference on the frequency, can be used as the fingerprint mark of qualification different molecular in Raman spectrum analysis.
(4) incident light source: the incident light source that commercialization Raman spectroscopy instrument is commonly used is LASER Light Source, the general LASER Light Source being equipped with 780nm and 532nm two kinds of wavelength.The excitation energy of 532nm light source is higher than 780nm light source.The molecule easily excited only needs 780nm light source just can be excited to produce Raman light, and the molecule being difficult to excite then needs 532nm light source just can be excited to produce Raman light.
(5) Raman frequency shift: Raman frequency shift is the difference on the frequency of incident light and Raman light, for describing the position of Raman bands of a spectrum, with wave number/cm
-1for unit.At present, the frequency displacement of Raman spectrum analysis scanning is interval general at 4000cm
-1~ 50cm
-1between.
(6) raman scattering intensity: for describing the intensity of Raman signal, mainly with cps(countspersecond) be unit.
4, Raman spectroscopy scans interpretation of result
The discovery at the Characteristic Raman peak of 4.1 waste oils and utilization
With 780nm laser the most frequently used at present for light source, scan all-band laman optical spectrum (specifically for refining " waste oil " DJ013 and soybean product oil ZC003) of refining " waste oil " and edible vegetable oil respectively, scanning result is as Fig. 1 and Fig. 2, visible by spectrum comparison, refining " waste oil ", though morphologically have significant difference with the Raman spectrum of edible vegetable oil, therefrom cannot be started with and find effective detection method.The applicant breaks through existing thinking limitation, observe the Raman spectrum not going out peak position at sample, using the higher 532nm laser of energy instead is light source, all-band laman optical spectrum (specifically for refining " waste oil " DJ013 and soybean product oil ZC003) of scanning refining " waste oil " and edible vegetable oil, scanning result is as Fig. 3 and Fig. 4, visible by spectrogram comparison, under 532nm light source, refining " waste oil " presents a huge obvious Characteristic Raman peak, and they are completely different from edible vegetable oil form.This Characteristic Raman peak has following distinguishing characteristics:
(1) morphological feature: at whole scanning wave band (3500cm
-1~ 50cm
-1) in, only there is a huge level and smooth bag-like Raman peaks in refining " waste oil ".This bag-like Raman peaks has great width, and its half-peak breadth reaches, and has even exceeded whole scanning wave band.
(2) strength characteristic: refining " waste oil " bag-like Raman peaks has great intensity, and its peak height (is positioned at 2000cm
-1near, be specially 2200cm
-1-1800cm
-1) intensity be more than or equal to 1.0 × 10
5(cps).
Through to existing related Raman peak spectrum data library searching, do not meet the record which kind of composition is this bag-like Raman peaks correspond to, and through to existing data of literatures library searching, do not meet the report of this bag-like Raman peaks for sample analysis.Thus can initial guess, this is a new Characteristic Raman peak, and it is huge bag-like, is to be formed by stacking by the Raman bands of a spectrum of Multiple components.
Further, be raw material with Various Seasonal, the meal kitchen waste grease that gives up that gathers from different location respectively, refining " waste oil " sample of 38 batches of preparation, scans their Raman spectrum (see Figure 17 and Figure 18) respectively under identical conditions with the incident laser light source of wavelength 532nm.Through comprehensive comparison, refining " waste oil " Characteristic Raman peak presents following characteristics:
(1) although the peak height of each refining " waste oil " sample characteristic Raman peaks and peak area difference, the form at their Characteristic Raman peaks is very close.
(2) all the peak position of refining " waste oil " sample characteristic Raman peaks is substantially identical, is all positioned at 2000cm
-1near, be specially 2200cm
-1-1800cm
-1, and the tendency of whole Raman peaks curve is also substantially identical, and improper composition corresponding to representation feature Raman peaks is not only substantially identical on composition, and also substantially identical in ratio between each composition.
(3) because above-mentioned refining " waste oil " sample is for raw material with different meal kitchen waste greases, prepared by refining condition (when the proterties such as kitchen waste grease acid value, smell, impurity of eating are different, deodorization used during " waste oil " refining, depickling, decolorization condition also can change thereupon) on demand.In conjunction with above-mentioned result, can think that the difference of raw material and refining condition is less to the scale effect between the composition of the form at refining " waste oil " Characteristic Raman peak and the improper composition of correspondence thereof and each composition.This Characteristic Raman peak visible all stable existence and can be used for being different from edible oil in various waste oil.
Based on the discovery at above-mentioned Characteristic Raman peak, we are to soy bean oil and product oil, vegetable seed crude oil, tea-seed oil, edible blend oil, olive product oil, peanut product oil, mustard seed product oil, palm crude oil and refined palm oil, sunflower seed crude oil and sunflower seed product oil, crude maize oil and corn product oil, refined coconut oil, rice bran crude oil, cottonseed crude oil, rice product oil, linseed product oil, sesame oil, the incident laser light source of Chinese prickly ash product oil wavelength 532nm carries out Raman spectroscopy scans, obtain respective Raman spectrum, see Figure 17-39, they are compared known with Figure 17 with 18, the form of Raman spectrum and they there is significant difference, be highly susceptible to differentiating.Although compare roughly, the Characteristic Raman peak (Figure 17) of refining " waste oil " to the Raman spectrum (Figure 38) of sesame oil although form comparatively similar, if carefully compare Figure 18 and Figure 39, both morphologically still have certain difference.Particularly at 3500cm
-1-3000cm
-1interval, refining " waste oil " Characteristic Raman peak curve presents the level and smooth trend risen, and the Raman peaks curve of sesame oil then presents the trend first declining and rise.
Therefore, also refining " waste oil " and sesame oil can effectively be differentiated completely based on Raman peaks form.
In addition, utilize Characteristic Raman peak, we can also differentiate the food plant crude oil that refining " waste oil " is blent.In the ratio of 10%, 30%, 50%, refining " waste oil " (DJ013) is mixed soy bean oil, crude maize oil, rice bran crude oil, cottonseed crude oil respectively, (result is see Figure 40-Figure 47 to scan the Raman spectrum respectively blending oil sample, wherein, respectively have 5 curves in Figure 41,43,45,47, it represents that the incorporation of waste oil is 100%, 50%, 30%, 10%, 0% from top to bottom respectively).Result shows, when the mixed ratio of refining " waste oil " is volume ratio 10%, the Raman spectrum blending oil sample presents the form at the Characteristic Raman peak of refining " waste oil " substantially, and the intensity of Raman peaks is also significantly higher than the Raman peaks of vegetable oils itself.Along with the increase of the incorporation of refining " waste oil ", the Raman spectrum form of blending oil sample is more similar to the Characteristic Raman peak of refining " waste oil ", and the intensity of Raman peaks is also with the trend that mixed ratio increases in gradient.
Further, by volume refining " waste oil " (DJ013) is mixed peanut product oil, rice product oil, corn product oil, olive product oil, soybean product oil by the ratio of number percent 10%, 30%, 50% respectively again, the Raman spectrum that oil sample is respectively blent in scanning (the results are shown in Figure 48-Figure 57, wherein, respectively have 5 curves in Figure 49,51,53,55,57, it represents that the incorporation of waste oil is 100%, 50%, 30%, 10%, 0% from top to bottom respectively).Result shows, with above blend compared with vegetable oils, the plant product oil blent of refining " waste oil " because of the change trend of the Raman spectrum form of mixing refining " waste oil " and causing and intensity identical, but plant product oil mix refining waste oil after Raman spectrum to change degree more remarkable.
The analysis of the character of the improper composition of 4.2 pairs of waste oils
The Raman spectrum superposition that refining " waste oil " DJ013 and the scanning of soybean product oil ZC003 Different Light obtain is obtained Fig. 5 and Fig. 6, and respectively infrared absorption spectrometry is carried out to these samples, obtain Fig. 7 and Fig. 8.Can find out by analysis, edible vegetable oil normal components is all that some can be excited to produce the molecule of Raman scattering under 780nm light source, it is the molecule easily excited, the improper composition of refining " waste oil " is then that some just will can be excited to produce at 532nm light source the molecule of Raman scattering, is the molecule being difficult to excite.The theory of Ramam effect is thought, the Raman active of molecule derives from the polarizability change that molecule produces under photon induced.Molecule produces the complexity of Raman scattering, depends on that molecule is induced the complexity polarized.General, large molecule, with the molecule of functional group, be easily induced to produce polarization, concrete example is as carbonyl group (3100cm
-1), C-H bond (3100cm
-1-2700cm
-1), cis C=C double bond (3009cm
-1), methylene (2923cm
-1and 2835cm
-1), ester bond carbonyl group (2500cm
-1-1600cm
-1), CH2 group (1464cm
-1), CH3 group (1377cm
-1), carbon oxygen singly-bound (1160cm in ester bond
-1, 1118cm
-1, 1095cm
-1, 1030cm
-1), trans-fatty acid (960cm
-1), chain alkyl (722cm
-1) etc. group; Otherwise Small molecular, the especially non-polar molecule that is made up of same atoms of two ends, as the molecule with chemical bonds such as C-C, C=C, N=N, S-S, relative difficult induction produces polarization.Therefore, therefrom can reach a conclusion, in edible oil, the overwhelming majority is all more above-mentioned large molecules or the molecule with functional group, and except containing, for example except the same above-mentioned normal components of edible oil in waste oil, also there is improper composition, this improper composition is very likely some relatively little non-polar molecules, and these molecular structures are similar, make the complexity basic simlarity not only producing Raman scattering, but also it is poor to have close vibration energy state, thus make them produce the very close Raman bands of a spectrum of frequency shift value, in addition these Small molecular content are very abundant, therefore, mutual combination is superimposed and creates huge bag-like Raman peaks.
Further, by Fig. 7 and 8, we can see, refining " waste oil " and edible vegetable oil have identical infrared spectrum.The improper composition be present in a large number in refining " waste oil " does not demonstrate any infrared active.This experimental result shows, improper composition is that some Raman scatterings are very strong, and the molecule that infrared absorption is very weak is exactly very likely the molecule with chemical bonds such as C-C, C=C, N=N, S-S, ring-types.The result that this result and the above-mentioned molecular structure to improper composition are inferred matches, thus provides favourable evidence for the structure prediction of refining " waste oil " improper composition.
The analysis in the source of the improper composition of 4.3 pairs of waste oils
Under 532nm LASER Light Source, to the meal kitchen waste grease gathered, frying raw material scanning Raman spectrum such as waste grease, animal waste grease (see Fig. 9-Figure 11).From Raman peaks form and intensity, the raw materials such as meal kitchen waste grease, frying waste grease and animal waste grease are all containing the improper composition similar to refining " waste oil ".Wherein the highest with the content of " waste oil " improper composition in the waste grease of kitchen of eating, its Characteristic Raman peak intensity is frying waste grease and animal waste grease more than 10 times (see Figure 12) respectively.Infer according to the production process of meal kitchen waste grease, storage requirement and physicochemical character: perhaps become sour, ferment, enzymolysis, the factor such as microorganism and washing agent also exist destruction again to waste grease.Wherein, perhaps make the carbochain of long-chain fatty acid rupture to produce the general Small molecular with chemical bonds such as C-C is cause the content of the improper composition of meal kitchen waste grease far above the main cause of other raw materials.
Under 532nm LASER Light Source, Raman spectrum is scanned to the refining " waste oil " prepared through deodorization, depickling, each refinement step of decolouring.See Figure 13-Figure 14, wherein, four curves of spectrum are from top to bottom expressed as follows the thick waste oil in stage respectively: after deodorization, after deodorization depickling, after deodorization depickling decolouring, without the waste grease of refining.As seen from the figure, meal kitchen waste grease (DM039, DM040) is after deodorization step, and the intensity at its Characteristic Raman peak is high to all having occurred the phenomenon that summit overflows; These samples are again after alkali-refining deacidification, adsorption bleaching step, and the intensity at its Characteristic Raman peak falls after rise to some extent, but still is much higher than raw material.Visible, in three steps of refining, deodorization step has the effect of improper component content in significant increase refining sample, alkali-refining deacidification and adsorption bleaching two step then have the effect reducing improper component content in refining sample, concrete reason may be in alkali-refining deacidification process, while a large amount of generation saponified is deposited in removing oil sample free fatty acid, also can due to improper composition partly in the effect removing oil sample of parcel and co-precipitation.Equally, in adsorption bleaching process, the adsorbents such as activated charcoal in removing oil sample while various pigment, also can remove the improper composition of part in oil sample due to suction-operated.But after three steps complete, the content of the improper composition of refining " waste oil " sample is still much higher than unrefined meal kitchen waste grease.
Further, in order to analyze the impact of high temperature distillation deodorization refining process on refining " waste oil " improper component content, have selected edible blend oil (heat stable oil plant) respectively and peanut oil (to heat sensitive oil kind), as raw material, carries out high-temperature heating test.Edible blend oil only experiences heating process, respectively processes 15min 100 DEG C, 150 DEG C, 200 DEG C and 250 DEG C.The still-process of whole airtight anaerobic then simulated by peanut oil, experiences 260 DEG C of process 120min.To the above-mentioned Sample Scan Raman spectrum (see Figure 15-Figure 16) heated through different temperatures.Scanning result shows, and edible blend oil does not produce and the plesiomorphic Raman peaks in refining " waste oil " Characteristic Raman peak after treatment of different temperature, and its Raman peaks intensity heating sample also has no growth; After peanut oil experiences 260 DEG C of process 120min, its Raman peaks intensity is only increased less than 1 times than raw material, and the form of its Raman peaks does not change, and the Raman peaks of its carbonyl group (is positioned at 3100cm
-1near) still occur.Result shows that carrying out high-temperature heating to grease can not produce improper composition in a large number.
Since high-temperature heating can not produce improper composition in a large number, improper composition after " waste oil " deodorization is so allowed to roll up and separately must have reason.The refining experiment of " waste oil " shows, the process of deodorization can remove the volatilizable malodorous elements of oil sample in a large number, also can remove wherein lower boiling composition in a large number, as free fatty acid, moisture and various impurity etc., thus make grease obtain purifying.In this course, the composition that can be dissolved in grease also will obtain significantly enrichment and concentrate.Experimental result above about improper composition Raman scattering active is pointed out, and the improper composition of the overwhelming majority is likely the non-polar molecule that number molecular weight is less.So, they have fat-soluble, and can obtain in grease purge process enrichment and concentrated also just very likely.Equally, depickling and decolorization process also have the effect of removal of contamination and purifying grease.Although it can reduce the absolute magnitude of improper composition in sample, along with the increase of grease proportion in the sample to which, in sample, the relative content of improper composition still can maintain higher level.According to the measuring and calculating of refining experiment result, whole deodorization, depickling, decolorization almost will remove the impurity accounting for raw material total amount more than 50%.Therefore, whole refining process is the process that grease obtains significantly purifying, is also that liposoluble constituent obtains significantly enrichment and concentrated process simultaneously.This may be exactly in refining " waste oil " sample improper composition all the time far above the main cause of its material sample.
Grease expert think, recycled wood materials is all through the oil that heating for multiple times uses.Edible oil and fat are once use or after discarding, its original safeguard measure is removed, a large amount of contact oxygen, light, heat, microorganism, enzymatic oxidation material and deterioration environment, often autoxidation, photooxidation, the interleaved parallel such as enzymatic oxidation, Oxidation of Fat and Oils is made to complete induction period rapidly, enter the accelerated oxidation stage, waste grease is caused to become the grease of deep oxidation, dehydrogenation, cyclisation, addition, cracking, the complex reactions such as polymerization produce the oxidation product of large amount of complex, comprise the superoxide of various fatty acid and grease accompaniment thereof, lysate, isomeric compound, cyclisation thing, polymkeric substance etc.Testing result shows, in recycled wood materials fatty acid composition, the ratio of low carbon number fatty acid (C≤14) significantly increases, and its content exceedes national standard more than 5 times, is up to 20 times.
And nutritionist thinks, the oxidation reaction of above-mentioned grease, and these react the polymerization that produces and cyclisation product is only " waste oil " the most fatal factor.On the one hand, deep oxidation reaction has made original nutritional labeling in edible oil and fat, as vitamin and essential fatty acid lose totally; On the other hand, studies have found that, eat the oil of this heating for multiple times, have relation with a lot of disease, as fatty liver, high fat of blood, hypertension, Crohn disease, cholecystitis, stomach trouble, obesity, even may increase the generation of heart disease and kinds cancer.Mournful, also do not have a kind of effective method can capture necessary being and the contents level of above-mentioned various grease deep oxidation product up to now comprehensively.Trace it to its cause, perhaps be because deep oxidation product is numerous, content is uneven, more crucially, between each deep oxidation product, proterties between deep oxidation product to grease normal components is too similar, and the instrument analytical method (as gas-matter, liquid-matter, nuclear magnetic resonance, absorption spectrum etc.) that employing is commonly used is difficult to each deep oxidation product in separated island form grease.
Through retrieval, the oxidation product overwhelming majority of grease is all the molecule with chemical bonds such as C-C, C=C, N=N, S-S, ring-types, and the molecule with this class formation is exactly the extremely strong molecule of Raman active just.Can infer, the Characteristic Raman peak of refining " waste oil " should comprise the Raman peaks of grease deep oxidation product, and perhaps they are exactly the main body of refining " waste oil " improper composition.From this meaning, the Characteristic Raman peak of refining " waste oil " is the mark that can characterize deep oxidation product necessary being and contents level overall picture in recycled wood materials at present.
4.4 reappearance tests
Select edible blend oil (ZC006) and refining " waste oil " (DJ013) as revision test sample, under the same conditions, to same sample duplicate measurements 10 times, the Raman spectrum (see Figure 58-Figure 59) of scanning each sample.Result shows, no matter is edible blend oil or refining " waste oil ", and any change does not occur the form of the Raman spectrum that multiple scanning obtains, but its intensity has certain change.
Select edible blend oil (ZC006) and refining " waste oil " (DJ013) as revision test sample, under the same conditions, repeated sampling 5 times in operation sequence, the respectively Raman spectrum (see Figure 60-Figure 61) of scanning samples.Result shows, for the refining " waste oil " of edible blend oil, repeatedly sampling is carried out the reappearance measured and is repeatedly measured same sample substantially identical in operation sequence, represents that the operating process such as sampling, sample introduction of oil sample affects less on the measured value of Raman spectrum.
4.5 accuracy testing
4.5.1 the efficiency assessment of reference sample
(1) vegetable oils reference sample: included current 12 common large class vegetable oils products, various product have collected 61 parts, the sample of Different sources, different batches, concrete representative preferably; Vegetable oils product is provided by the edible vegetable oil manufacturing enterprise of largest domestic type, and from the horse's mouth, information is complete.
(2) food plant product oil reference sample: included current 14 common large class food plant finished oil product, various product have collected 109 parts, the sample of Different sources, different batches, concrete representative preferably; Food plant finished oil product is purchased from Ge great supermarket, Shenzhen, and from the horse's mouth, information is complete.
(3) recycled wood materials reference sample: meal kitchen waste grease 40 parts, frying waste grease 24 parts, animal waste grease 3 parts.The enterprise that changing food waste centrally disposes that is engaged in that the meal kitchen waste grease of different batches is specified from government divides the four seasons to gather.The hotel of these enterprises more than 600 towards whole city different flavor and characteristic, restaurant and dining room, the meal kitchen waste grease sample of recovery has good diversity and representativeness.
(4) refining " waste oil " reference sample: adopt " waste oil " criminal gang at present the most frequently used and be easy to get most raw material, most possibly and be ready most employing refinery practice route, prepared 38 parts, refining " waste oil " sample in batches.The refinement step such as the raw material adopted and deodorization, depickling, decolouring all have ubiquity and representativeness.Even if criminal gang adopts the process conditions being different from this, as long as they adopt recycled wood materials to be raw material, the content of the improper composition in its refining of producing " waste oil " only can be higher than raw material, can not be lower than raw material, more can not make it to disappear.
4.5.2 sample survey
(1) with 61 parts of food plant crude oil, 109 parts of plant product oil samples for edible vegetable oil testing sample; Mixing with 60 parts the various oil samples that 10%, 30%, 50% refining " waste oil " blends respectively is " waste oil " testing sample.
(2) under identical conditions, scan the Raman spectrum of each edible vegetable oil testing sample and " waste oil " testing sample respectively, collect the spectrogram of each sample.
(3) 61 parts of food plant crude oil, 109 parts of plant product oil samples are showed no the Characteristic Raman peak of refining " waste oil ", are judged to feminine gender.
(4) 60 parts mix 10%, 30%, 50% refining " waste oil " blend the Characteristic Raman peak that sample all presents refining " waste oil ", be judged to the positive.
In summary, this method has following technical advantage:
(1) accurate, sensitive, applicable.Refining " waste oil " and various food plant crude oil, food plant product oil can be differentiated, also can differentiate to mix the various oil and fat products being low to moderate 10% refining " waste oil " and blending, be showed no false positive and false negative result.
(2) easy, quick, low cost.Sample, without the need to pre-treatment, can can't harm and directly measure all kinds of oil sample; Measure that a sample is consuming time is no more than 1min; The price of required Raman spectrometer is no more than 500,000 yuan, and testing process does not consume any reagent and material substantially.
(3) edible vegetable oil production-supply-marketing and use relevant enterprise, utilize this method to be expected the inspection realizing raw material, product and commodity grease being carried out to all standing, effectively intercept " waste oil " and illegally flow into regular edible vegetable oil producing, processing and selling and intermediate links.
(4) food safety Regulation department and related check mechanism, utilizes this method to be expected the inspection realizing the edible oil and fat of market circulation and use being carried out to hauling type, hits the illegal activity that " edible oil " is made and sold in utilization " waste oil " effectively.
(5) Disease Prevention and Control Institutions and related research institutes, utilize this method be expected to realize to grease associated sample carry out on a large scale with the monitoring of large sample amount, provide basic data for assessing the epidemic status of " waste oil ", hazards identification and health risk.
Meanwhile, described detection method also has following significance:
(1) from refining " waste oil ", found a new Characteristic Raman peak, this Characteristic Raman peak is produced by ubiquitous in refining " waste oil ", that content is very abundant improper composition.
(2) confirm that refining " waste oil " and edible vegetable oil exist greatest differences on composition first.Be mainly manifested in refining " waste oil " containing very abundant improper composition, and substantially there is no this composition in edible vegetable oil.Whether this discovery has difference about refining " waste oil " and edible vegetable oil for cracking on composition, has which kind of difference, and difference degree how, and the sciences problems of this long-standing problem academia provides strong evidence.
(3) found that the improper composition of refining " waste oil " is one group and is produced in use and waste procedures by edible oil and fat, structure and proterties and the diverse Small molecular of edible vegetable oil normal components.Deep oxidation product in these Small molecular and recycled wood materials has higher relevance.This is found to be explores improper composition in recycled wood materials further, comprise the overall picture of deep oxidation product necessary being and contents level, and they is to the harm of humans and animals health and risk, provides important mark and guiding.
(4) found that refining " waste oil " obtains enrichment and concentrated feature and rule from raw material to the improper composition of finished product overall process, prove that the improper composition of refining " waste oil " not only can not be cut down due to refining or disappear, be that refinement is higher on the contrary, the content of its improper composition is higher.Which kind of processes refining " waste oil " no matter lawless person adopt, as long as this process relates to the purifying to grease, all cannot reduce or eliminate its improper composition.This discovery brings hope for cracking the global problem that refining " waste oil " detects.
(5) found that refining " waste oil " Characteristic Raman peak has form uniqueness, intensity is high, is easy to measure, without the need to distinguishing features such as sample pre-treatments.Utilize this Characteristic Raman peak both can set up the inspection technology differentiating refining " waste oil " from oil sample, also can explore and detect in all kinds of sample, as the method for " waste oil " improper composition in the samples such as food, feed, blood, body fluid, excreta, for monitoring and evaluation refining " waste oil " improper composition is in the service of the exposed amount of humans and animals, intake, excretion, storage allowance, distribution situation and agent effect relationship.
Annex one
Annex two
Annex three
| Sample number into spectrum | Date of manufacture | Quantity |
| DJ003 | 2012-12-20 | 250ml |
| DJ004 | 2013-4-23 | 500ml*2 |
| DJ005 | 2013-4-23 | 500ml*2 |
| DJ006 | 2013-4-23 | 500ml*2 |
| DJ008 | 2013-4-28 | 500ml*2 |
| DJ009 | 2013-5-12 | 500ml |
| DJ010 | 2013-6-4 | 250ml |
| DJ012 | 2013-6-5 | 300ml |
| DJ013 | 2013-6-5 | 300ml |
| DJ014 | 2013-7-3 | 200ml |
| DJ015 | 2013-7-3 | 200ml |
| DJ016 | 2013-7-4 | 300ml |
| DJ017 | 2013-7-4 | 300ml |
| DJ018 | 2013-7-5 | 400ml |
| DJ019 | 2013-7-5 | 300ml |
| DJ020 | 2013-7-10 | 500ml |
| DJ021 | 2013-7-19 | 300ml |
| DJ022 | 2013-7-25 | 200ml |
| DJ023 | 2013-7-26 | 150ml |
| DJ024 | 2013-7-31 | 300ml |
| DJ025 | 2013-7-11 | 200ml |
| DJ026 | 2013-8-8 | 400ml |
| DJ027 | 2013-8-22 | 250ml |
| DJ028 | 2013-8-22 | 150ml |
| DJ033 | 2013-8-30 | 350ml |
| DJ034 | 2013-8-30 | 150ml |
| DJ035 | 2013-8-30 | 220ml |
| DJ036 | 2013-8-30 | 70ml |
| DJ037 | 2013-8-30 | 220ml |
| DJ038 | 2013-9-19 | 350ml |
| DJ039 | 2013-9-19 | 200ml |
| DJ040 | 2013-9-19 | 15ml |
| DJ041 | 2013-10-9 | 200ml |
| DJ042 | 2013-10-9 | 200ml |
| DJ043 | 2013-10-9 | 200ml |
| DJ044 | 2013-10-10 | 200ml |
| DJ045 | 2013-10-10 | 200ml |
| DJ046 | 2013-10-10 | 200ml |
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. detect a method for waste oil based on Raman spectroscopy, it is characterized in that, comprise following detecting step:
Adopt the incident laser light source of 532nm wavelength to carry out Raman spectroscopy scans to refining waste oil, obtain the Raman spectrogram of refining waste oil, determine the Characteristic Raman peak of described refining waste oil; Wherein, described Characteristic Raman peak is positioned at the interval 1800cm of Raman frequency shift
-1-2200cm
-1, its peak curve is level and smooth bag-like, and the half-peak breadth at described Characteristic Raman peak has exceeded the interval 3500cm of Raman frequency shift
-1-50cm
-1;
Adopt the incident laser light source of 532nm wavelength to carry out Raman spectroscopy scans to oil sample to be measured, obtain the Raman spectrogram of oil sample to be measured; The Raman spectrogram of the Raman spectrogram of described oil sample to be measured and described refining waste oil is contrasted, when described Characteristic Raman peak appears in described oil sample to be measured, judges that described oil sample to be measured contains waste oil.
2. the method detecting waste oil as claimed in claim 1, it is characterized in that, when the laser energy of Raman spectroscopy scans is 5.0mW, the intensity at described Characteristic Raman peak is more than or equal to 1.0 × 10
5cps.
3. the method detecting waste oil as claimed in claim 1, it is characterized in that, oil sample to be measured is being carried out in the step of Raman spectroscopy scans, repeatedly scanning can be sampled to oil sample to be measured, and each scanning curve is placed in same Raman spectrogram, the Raman spectrogram of the oil sample described to be measured formed after obtained each sample curve combining.
4. the method for the detection waste oil as described in claim 1 or 3, it is characterized in that, in the step at Characteristic Raman peak determining waste oil, sampling scanning can be carried out by the various refining waste oils different to raw materials, and each sample scanning curve is placed in same Raman spectrogram, the Raman spectrogram of the described refining waste oil formed after obtained curve combining.
5. the method for the detection waste oil as described in claim 1 or 3, is characterized in that, the raw materials of described refining waste oil is waste oil crude oil, and described waste oil crude oil is at least one in meal kitchen waste grease, frying waste grease, animal waste grease.
6. the method detecting waste oil as claimed in claim 1, it is characterized in that, described oil sample to be measured comprises edible vegetable oil, and described edible vegetable oil is at least one in soy bean oil and product oil thereof, vegetable seed crude oil, tea-seed oil, edible blend oil, olive product oil, peanut oil, sesame oil, mustard seed product oil, palm crude oil, refined palm oil, sunflower seeds crude oil and product oil, crude maize oil and product oil thereof, refined coconut oil, rice bran crude oil, cottonseed crude oil, rice product oil, refining safflower oil, linseed product oil, Chinese prickly ash product oil.
7. the as claimed in claim 1 method detecting waste oil, it is characterized in that, described oil sample to be measured comprises blends oil, described in blend in oil, be at least the waste oil of 10% containing percent by volume.
8. the as claimed in claim 7 method detecting waste oil, is characterized in that, described in blend oil for the edible vegetable oil containing waste oil.
9. the method detecting waste oil as claimed in claim 1, is characterized in that, described refining waste oil is obtained through deodorization, depickling, decolouring by waste oil crude oil.
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