CN110044946A - A kind of method of low-field nuclear magnetic resonance measurement carbon black oil content - Google Patents
A kind of method of low-field nuclear magnetic resonance measurement carbon black oil content Download PDFInfo
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- CN110044946A CN110044946A CN201910430597.6A CN201910430597A CN110044946A CN 110044946 A CN110044946 A CN 110044946A CN 201910430597 A CN201910430597 A CN 201910430597A CN 110044946 A CN110044946 A CN 110044946A
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- G01N24/00—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects
- G01N24/08—Investigating or analyzing materials by the use of nuclear magnetic resonance, electron paramagnetic resonance or other spin effects by using nuclear magnetic resonance
- G01N24/082—Measurement of solid, liquid or gas content
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Abstract
The present embodiments relate to a kind of methods of low-field nuclear magnetic resonance measurement carbon black oil content, which comprises the working curve of production carbon black oil content；Calculate the working curve equation of carbon black oil content；Measurement carbon black sample quality and the oil quality for calculating carbon black sample；And calculate the oil content of carbon black sample.This method is suitable for the various carbon black products produced using coal tar, ethylene bottom oil, carbolineum etc. as raw material.The present invention uses feedstock oil to calibrate sample for carbon black oil content, reaches the accuracy and validity of the measurement of carbon black oil content.This method has many advantages, such as that the accurate precision of measurement is high, stability is good, time-consuming is short, and sample preparation is simple, safe operation, and process is simple.
Description
Technical field
The present invention relates to nmr analysis fields, and in particular to a kind of low-field nuclear magnetic resonance measurement carbon black oil content
Method.
Background technique
Carbon black is a kind of amorphous carbon, is carbonaceous material (coal, natural gas, heavy oil, fuel oil etc.) in the item of lack of air
Through imperfect combustion or product obtained by being thermally decomposed under part.Carbon black can make black dyes, for manufacturing Chinese ink, ink, oil
Paint etc., moreover it can be used to which the reinforcing agent for doing rubber is indispensable raw material in rubber industry.World rubber industry raw material consumption
What dosage made number one is raw rubber, and second is carbon black.In other words, carbon black has become the maximum rubber chemicals of consumption figure.
Carbon black is mainly generated by feedstock oils such as coal tar, heavy oil by burn incompletely.Due to carbon black feed stock oil quality
And the control problem of production technology, the generally existing carbon black products adsorption of furnace black production line have incomplete cracking reaction
Aromatic oil has seriously affected the compatibility of carbon black and macromolecule resin material, and the homininoxious body of aromatic oil is strong
Health does not meet environmental requirement.Having 16 substances in polycyclic aromatic hydrocarbon is considered as the compound of insalubrity, since it has by force
Causing toxicity, mutagenesis and the characteristics such as carcinogenic, the content of polycyclic aromatic hydrocarbon has caused to pay attention to extensively in carbon black.In addition, carbon black contains
Oil cut rate is excessively high, is also easy to that rubber product is caused to occur spraying blue phenomenon, largely effects on the quality of rubber.
Method currently used for evaluating carbon black oil content is the measurement using toluene light transmittance.Firstly, by carbon black pellet with
Toluene mixing, is dissolved into the finish composition on surface in toluene, then measure the light transmittance of toluene, by the size of light transmittance come
How much is the content of reflection finish.But this method can only measure the finish of carbon blacksurface, and there is operating procedure complexity, measurement
As a result inaccurate, big to the injury of personnel using toxic inflammable solvent, there is pollution to environment.
In addition, other conventional techniques also all can not oil content effectively in Accurate Determining carbon black, this be mainly based upon with
Under several reasons:
The first, the oil content of carbon black is very low, is lower than 1%, and the distribution of oil is likely to be present in particle surface and may also be wrapped
It is rolled in inside particle.
The second, all fine to the absorbability of various visible lights and infrared light since carbon black is black powder, it is difficult to use spectrum
Technology come detect oil content.
Third, the surface area of carbon black are very big, and adsorptivity is especially good, and dispersibility in a solvent is also fine, it is more difficult to often
The extraction of rule come measure oil content.
4th, carbon black also has certain electric conductivity, and size, the state of electric conductivity and particle are all related, and due to containing
Oil cut rate is especially low, and conventional electrical conductivity method and capacitance method are all invalid.
In addition, carbon black is a kind of powdered substance of particle very little, and state big to the injury of the respiratory mucosa of human body
The substance for having carcinogenic risk generally acknowledged on border.Therefore, seek a kind of method that safely and effectively can accurately detect carbon black oil content,
Have become the urgent requirement of carbon black industry development.
Summary of the invention
Nuclear magnetic resonance technique is a kind of effective means for detecting organic matter, the protium in its main detecting organic compounds.Mesh
Preceding high-field nuclear magnetic resonance technology is widely used in scientific research, field of medical imaging；Low-field nuclear magnetic resonance technology agricultural food product,
The fields such as textile fabric, oil exploration are also widely used.Carbon black be it is a kind of main carbon containing, containing a small amount of hydrogen, oxygen and ash content
Substance, theoretically it should be a kind of ideal nuclear magnetic resonance research and measurement object；But it has been recognized that carbon black has one
Fixed electric conductivity, it can generate shielding action to the electromagnetic wave that nuclear magnetic resonance apparatus emits, therefore there is no carry out phase to carbon black
The research of pass and the report of test.
The applicant passes through the study found that the ingredient in carbon black mainly exists with graininess, although particle has portion
Divide electric conductivity, but whole is not complete conductor, so carbon black sample does not have any influence to radio frequency electromagnetic.Therefore, completely
Nuclear magnetic resonance technique research carbon black can be used.
However nuclear magnetic resonance is a kind of indirect measurement method again, measurement result needs to convert by correctly calibration
At correct oil content.Present applicant has proposed the working curve scaling methods and sample to be tested of the measurement of carbon black oil content as a result,
Oil content survey calculation method.
A kind of method for being designed to provide low-field nuclear magnetic resonance measurement carbon black oil content of the embodiment of the present invention, is applicable in
In the various carbon black products produced using oil Class such as coal tar, ethylene bottom oil, carbolineums as raw material.The present invention use feedstock oil for
Carbon black oil content calibrates sample, reaches the accuracy and validity of the measurement of carbon black oil content.This method have measure accurate precision it is high,
The advantages that stability is good, time-consuming short, and sample preparation is simple, safe operation, process is simple.
Specifically, the present invention provides a kind of method of low-field nuclear magnetic resonance measurement carbon black oil content, the method includes
The following steps:
(1) working curve of carbon black oil content is made；
(2) the working curve equation of carbon black oil content is calculated；
(3) it measures carbon black sample quality and calculates the oil quality of carbon black sample；And
(4) oil content of carbon black sample is calculated.
Further, step (1) specifically includes: raw material oil samples used in production of carbon black is taken, with low-field nuclear magnetic resonance point
Analyzer, the basal signal S of (m=0) when sample is not added in measurement first0；Then multiple addition different quality (m=m are measured respectivelyi)
Raw material oil samples, their signal amplitude is denoted as S respectivelyi；Using the quality of raw material oil samples as abscissa, signal amplitude is vertical
Coordinate draws SiAnd miScatter plot.
Further, measurement at least four adds different quality (m=m respectivelyi) raw material oil samples, and raw material oil samples
Mass Distribution is uniform.
Further, step (1) further include: take raw material oil samples used in production of carbon black, measure its T2 with CPMG sequence
Map calculates the geometrical mean T2g of T2 according to T2 map.
Further, step (1) further include: at least take repetition of 5 times of the geometrical mean T2g as spin-echo sequence
Waiting time TW.If TW value is too small, measurement result is unstable.
Further, step (2) specifically includes: the working curve of carbon black oil content is calculated according to unary linear regression equation
Equation.
Further, step (3) specifically includes: taking carbon black sample to be measured, measures its mass M, use low-field nuclear magnetic resonance
Analyzer measures its signal strength S；Signal strength S is updated in the working curve equation of step (2), finds out carbon black sample
Mass M _ oil of oil.
Further, step (4) specifically includes: calculating the oil content of carbon black sample are as follows: M_oil/M × 100%.
The embodiment of the present invention has the advantages that
1, this method is suitable for the various carbon blacks productions produced using oil Class such as coal tar, ethylene bottom oil, carbolineums as raw material
Product.
2, it uses feedstock oil to calibrate sample for carbon black oil content, reaches the accuracy and validity of the measurement of carbon black oil content, solution
It has determined conventional measuring equipment and method insurmountable carbon black oil content measurement problem.
3, the easy to operate, safe and effective of this method, accuracy is high, repeated and stability is good.
Detailed description of the invention
It, below will be to embodiment party in order to illustrate more clearly of embodiments of the present invention or technical solution in the prior art
Formula or attached drawing needed to be used in the description of the prior art are briefly described.It should be evident that the accompanying drawings in the following description is only
It is merely exemplary, it for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer, which is extended, obtains other implementation attached drawings.
Structure depicted in this specification, ratio, size etc., only to cooperate the revealed content of specification, for
Those skilled in the art understands and reads, and is not intended to limit the invention enforceable qualifications, therefore does not have technical
Essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size are not influencing the function of the invention that can be generated
Under effect and the purpose that can reach, should all still it fall in the range of disclosed technology contents obtain and can cover.
Fig. 1 is the schematic diagram of carbon black oil content working curve provided by one embodiment of the present invention.
Fig. 2 is the T2 map that CPMG sequence provided by one embodiment of the present invention measures.Wherein abscissa indicates the T2 time,
Ordinate indicates corresponding amplitude, and the vertical line among wave crest indicates the position of T2g, to indicate T2g=120ms in figure.
Fig. 3 is the spin echo signal amplitude measurement schematic diagram of carbon black sample to be tested provided by one embodiment of the present invention.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily, it is clear that described embodiment is the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Embodiment 1
The method of carbon black oil content and -3 as follows referring to Fig.1 is measured in the present embodiment:
(1) raw material oil samples used in production of carbon black are taken, with low-field nuclear magnetic resonance analyzer, when sample is not added in measurement first
(m=0) basal signal S0；Then multiple addition different quality (m=m are measured respectivelyi) raw material oil samples, their signal
Amplitude is denoted as S respectivelyi；Using the quality of raw material oil samples as abscissa, signal amplitude is ordinate, draws SiAnd miScatter plot,
The working curve of carbon black oil content is made, as shown in Figure 1.
Using Larmor's nuclear magnetic resonance carbon black oil content analyzer, carbon black feed stock oil samples are taken first, are surveyed with CPMG sequence
Its T2 map is measured, as shown in Fig. 2, calculating the geometrical mean T2g of T2 according to T2 map.Then at least 5*T2g is taken (to be more than or equal to
5 times, measurement result is more accurate) repetition waiting time TW as spin-echo sequence.If TW value is too small, measurement result is not
Stablize.
(2) then, with spin-echo sequence, measure basal signal and several different qualities (0.78g, 1.47g,
1.99g, 2.61g, sample quality are evenly distributed as much as possible) the echo-signal amplitudes of raw material oil samples, as shown in Figure 3.Rendering quality
It with the scatter plot of signal, then goes to be fitted with a linear equation, calculates regression equation, it is bent to obtain so-called standard work
Line calculates the working curve equation of carbon black oil content.
(3) it measures carbon black sample quality and calculates the oil quality of carbon black sample: taking carbon black sample to be measured, it is net to measure it
Weight M, then measures the amplitude S of echo-signal with the spin-echo sequence of step (2).According to working curve, it is corresponding to calculate signal S
Oil-containing mass M _ oil.
(4) oil content of carbon black sample is calculated are as follows: M_oil/M × 100%.
This method solve conventional measuring equipments and the insurmountable carbon black oil content of method to measure problem, the behaviour of this method
It is good to make simple, safe and effective, accuracy height, repeatability and stability.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (8)
1. a kind of method of low-field nuclear magnetic resonance measurement carbon black oil content, which is characterized in that the method includes the following steps:
(1) working curve of carbon black oil content is made；
(2) the working curve equation of carbon black oil content is calculated；
(3) it measures carbon black sample quality and calculates the oil quality of carbon black sample；And
(4) oil content of carbon black sample is calculated.
2. the method according to claim 1, wherein step (1) specifically includes: taking raw material used in production of carbon black
Oil samples measure basal signal S when sample is not added with low-field nuclear magnetic resonance analyzer first0；Then multiple add is measured respectively
Add the raw material oil samples m of different qualityi, their signal amplitude is denoted as S respectivelyi；Using the quality of raw material oil samples as abscissa,
Signal amplitude is ordinate, draws SiAnd miScatter plot.
3. according to the method described in claim 2, it is characterized in that, measurement at least four adds the feedstock oil of different quality respectively
Sample, and feedstock oil sample quality is evenly distributed.
4. according to the method described in claim 2, it is characterized in that, step (1) further include: take feedstock oil used in production of carbon black
Sample measures its T2 map with CPMG sequence, and the geometrical mean T2g of T2 is calculated according to T2 map.
5. according to the method described in claim 4, it is characterized in that, step (1) further include: at least take 5 times of geometrical mean
Repetition waiting time TW of the T2g as spin-echo sequence.
6. the method according to claim 1, wherein step (2) specifically includes: according to unary linear regression equation
Calculate the working curve equation of carbon black oil content.
7. the method according to claim 1, wherein step (3) specifically includes: taking carbon black sample to be measured, survey
Its mass M is measured, measures its signal strength S with low-field nuclear magnetic resonance analyzer；Signal strength S is updated to the work of step (2)
In curvilinear equation, mass M _ oil of the oil of carbon black sample is found out.
8. the method according to claim 1, wherein step (4) specifically includes: calculating the oil-containing of carbon black sample
Rate are as follows: M_oil/M × 100%.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103362505A (en) * | 2012-04-10 | 2013-10-23 | 中国石油化工股份有限公司 | Method for judging and identifying drilling-encounter oil layer under condition that drilling fluid adding oil exists |
| CN103728197A (en) * | 2014-01-07 | 2014-04-16 | 江苏长乐纤维科技有限公司 | Method for detecting moisture content and oil content of fibers |
| US20150130460A1 (en) * | 2013-11-13 | 2015-05-14 | Schlumberger Technology Corporation | Methods for separating oil and water on multidimensional nuclear magnetic resonance maps |
| CN104777181A (en) * | 2014-12-31 | 2015-07-15 | 中国石油天然气股份有限公司 | Nuclear magnetic resonance T of dense oil2Cutoff value and fluid saturation determination method and device |
| CN106442599A (en) * | 2016-08-31 | 2017-02-22 | 中国石油天然气股份有限公司 | Method and device for measuring oil content of rock |
| CN107843611A (en) * | 2016-09-20 | 2018-03-27 | 中国石油化工股份有限公司 | Low permeability sandstone reservoir moveable gel nuclear magnetic resonance parameter characterizes new method |
| CN109696450A (en) * | 2019-01-17 | 2019-04-30 | 南京林业大学 | A kind of method of enabling non-destructive determination simple grain vegetable seeds oil content |
-
2019
- 2019-05-22 CN CN201910430597.6A patent/CN110044946B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103362505A (en) * | 2012-04-10 | 2013-10-23 | 中国石油化工股份有限公司 | Method for judging and identifying drilling-encounter oil layer under condition that drilling fluid adding oil exists |
| US20150130460A1 (en) * | 2013-11-13 | 2015-05-14 | Schlumberger Technology Corporation | Methods for separating oil and water on multidimensional nuclear magnetic resonance maps |
| CN103728197A (en) * | 2014-01-07 | 2014-04-16 | 江苏长乐纤维科技有限公司 | Method for detecting moisture content and oil content of fibers |
| CN104777181A (en) * | 2014-12-31 | 2015-07-15 | 中国石油天然气股份有限公司 | Nuclear magnetic resonance T of dense oil2Cutoff value and fluid saturation determination method and device |
| CN106442599A (en) * | 2016-08-31 | 2017-02-22 | 中国石油天然气股份有限公司 | Method and device for measuring oil content of rock |
| CN107843611A (en) * | 2016-09-20 | 2018-03-27 | 中国石油化工股份有限公司 | Low permeability sandstone reservoir moveable gel nuclear magnetic resonance parameter characterizes new method |
| CN109696450A (en) * | 2019-01-17 | 2019-04-30 | 南京林业大学 | A kind of method of enabling non-destructive determination simple grain vegetable seeds oil content |
Non-Patent Citations (2)
| Title |
|---|
| 王志战 等: "利用NMR技术判识混油钻井液条件下钻遇的油层", 《波谱学杂志》 * |
| 蔡坚等: "核磁共振法测定高州油茶种仁含油率试验", 《林业科技开发》 * |
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