CN102323296A - Method for rapid detection of carbon, hydrogen, oxygen, nitrogen and sulfur in petroleum - Google Patents
Method for rapid detection of carbon, hydrogen, oxygen, nitrogen and sulfur in petroleum Download PDFInfo
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- CN102323296A CN102323296A CN201110262507A CN201110262507A CN102323296A CN 102323296 A CN102323296 A CN 102323296A CN 201110262507 A CN201110262507 A CN 201110262507A CN 201110262507 A CN201110262507 A CN 201110262507A CN 102323296 A CN102323296 A CN 102323296A
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Abstract
The invention belongs to the field of chemistry, and discloses a method for detection of carbon, hydrogen, oxygen, nitrogen and sulfur in petroleum. The method is characterized by comprising the following steps of (1) accurately weighing a petroleum sample, putting the petroleum sample into a tailor-made sample cup, and sealing up; (2) feeding helium gas, argon gas and oxygen gas into each 1mg of the petroleum sample, determining content of carbon, hydrogen, nitrogen and sulfur, feeding argon has and mixed gas of helium gas and hydrogen gas into each 1mg of the petroleum sample, and determining content of oxygen; and (3) carrying out high-temperature cracking of the petroleum sample and burning of the cracked petroleum sample in pure oxygen to convert carbon, hydrogen, oxygen, nitrogen and sulfur in the petroleum sample to CO2, H2O, CO, N2 and SO2; and (4) carrying out separation of CO2, H2O, CO, N2 and SO2 by a chromatographic column, and determining content of carbon, hydrogen, oxygen, nitrogen and sulfur by a thermal conductivity detector.
Description
Technical field
The invention belongs to chemical field, be applicable to the mensuration of carbon in the oil, hydrogen, oxygen, nitrogen, sulphur.
Background technology
Oil (petroleum) also claim crude oil, is a kind of thickness, dark brown liquid, and the main application of oil is to produce fuel oil, is the important source material of gasoline, diesel oil, kerosene, aviation wet goods fuel oil.Simultaneously, oil is the important source material of relevant chemical products still, is the raw material of industrial products such as organic solvent, lubricant, plastics, chemical fertilizer, pitch, paraffin, petroleum coke.Oil is important energy, industrial chemicals, and the oil of having exploited at present about 87% is used to the energy, and 13% is used for chemical industry.Oil is the lifeblood of human being's production, domestic energy, is the blood of chemical industry.
Because oil is a kind of non-renewable energy and industrial chemicals, the generation of oil needs the time in 2,000,000 years at least, and in the oil of verifying, finding, the time is the oldest reaches 500,000,000 years.In the historical progress that the earth constantly develops, after many Paleozoic Era and the Mesozoic a large amount of plant and animal death, organic substance constantly decomposes, deposits and forms oil gradually.Oil is organic mixture, mainly contains alkane, naphthenic hydrocarbon, aromatic hydrocarbon.Essential element is carbon, hydrogen, oxygen, nitrogen, sulphur etc., and carbon, hydrogen are the principal ingredient element of oil, and sulphur, oxygen, nitrogen and most compound thereof are the objectionable impuritiess in the oil, in oil refinery, process, should remove as far as possible.
The present invention is intended to overcome the defective of prior art, uses elemental analyser, detects carbon, hydrogen, oxygen, nitrogen, sulfur content in the oil, and measurement result is accurate, and finding speed is fast.Oil is the same with other organism; Mainly form by carbon, hydrogen, oxygen, nitrogen, sulphur and other poisonous metal element; The present invention studies the assay method of oxygen in the oil, carbon, hydrogen, nitrogen, sulphur, is intended to study the constituent of oil, and then studies its structure and characteristic; So that the utilization of oil refinery and petroleum chemical industry has unique novelty and practicality.
Summary of the invention
The assay method of carbon, hydrogen, oxygen, nitrogen, sulphur in the oil of the present invention, form by following steps:
One, accurate weighing oil sample places special aluminium quality sample cup, sealing;
Two, per 1 milligram of oil sample quantitatively feeds carrier gas (helium 0.14MPa), power gas (argon gas 0.4MPa), burning gas (oxygen 0.1MPa), measures carbon, hydrogen, nitrogen, sulphur;
Per 1 milligram of oil sample quantitatively feeds carrier gas (helium-hydrogen mixed gas 0.14MPa), power gas (argon gas 0.4MPa), measures oxygen;
Three, oil is through Pintsch process, burn in pure oxygen, and the carbon in the sample, hydrogen, nitrogen, sulphur change into gas CO
2, H
2O, N
2, SO
2
Oil is through Pintsch process, burn in helium-hydrogen mixed gas, and the oxygen in the sample changes into gas CO;
Four, CO
2, H
2O, CO, N
2, SO
2Separate through chromatographic column, thermal conductance detects carbon, hydrogen, oxygen, nitrogen, sulphur percentage composition.
PetroChina Company Limited. of the present invention sample burns in Pintsch process, pure oxygen after feeding carrier gas (helium), power gas (argon gas), burning gas (oxygen), and carbon, hydrogen, nitrogen, sulphur change into gas CO in the oil
2, H
2O, N
2, SO
2, separate through chromatographic column, carry out thermal conductance and detect, measure carbon, hydrogen, nitrogen, sulphur; The oil sample burns in Pintsch process, helium-hydrogen mixed gas after feeding carrier gas (helium-hydrogen mixed gas), power gas (argon gas), and oxygen changes into gas CO in the oil, separates through chromatographic column, and thermal conductance detects oxygen.
Elemental analyser is proofreaied and correct with the standard substance cystine, measures carbon, hydrogen, nitrogen, sulfur content in the oil; Proofread and correct with the standard substance benzoic acid, measure oxygen content in the oil.
Principal feature of the present invention:
1, the mensuration secondary of carbon, hydrogen, oxygen, nitrogen, five constituent contents of sulphur can be accomplished in the oil, the invention solves the fast measuring problem of carbon in the oil, hydrogen, oxygen, nitrogen, sulphur, and assay method is quick, accurate.
2, detection limit is low, satisfies oil and detects needs, carbon detection limit 0.02%, hydrogen detection limit 0.04%, oxygen detection limit 0.03%, nitrogen detection limit 0.04%, sulphur detection limit 0.04%.
3, measuring stability meets the requirements; Measure relative standard deviation (RSD): carbon 0.45～0.65%, hydrogen 1.44～2.05%, nitrogen 1.45～2.76%, sulphur 1.21～2.41%, oxygen 1.02～3.25%; Measure relative standard deviation RSD all less than 3.5%; Instrument measuring stability is better, and error at measurment is little.
4, measuring repeatability meets the demands; Carbon, hydrogen, oxygen, nitrogen, sulphur recovery of standard addition experimental result in the oil: carbon 90.1～112.8%, hydrogen 92.0～108.0%, oxygen 87.3～106.8%; Nitrogen 94.0～116.9%; Sulphur 87.1～105.3%, carbon, hydrogen, oxygen, nitrogen, sulphur recovery of standard addition scope 87.1～116.9%, it is accurate to measure the result.
5, except that copper powder, glass wool, platinum carbon, EA 6000 reductive agents etc., do not use other chemical reagent, environment is not had to pollute basically.
Embodiment
Embodiment 1:
1 uses instrument:
1.1 elemental analyser, model: EA 2400, U.S. PE company produces.
1.2 electronic balance is accurate to 0.001 milligram; Model: AD6, U.S. PE company produces.
2 use reagent
2.1 cystine standard substance constituent content: carbon 29.99%, hydrogen 5.03%, nitrogen 11.67%, sulphur 26.69% (being used to measure carbon, hydrogen, nitrogen, sulfur content instrumental correction).
2.2 benzoic acid standard substance constituent content: oxygen 26.20%, carbon 68.85%, hydrogen 4.95% (be used to measure the oxygen content instrumental correction, only use the content of oxygen).
2.3 high purity oxygen gas, purity is more than 99.995%.
2.4 high-purity argon gas, purity is more than 99.995%.
2.5 high-purity helium, purity is more than 99.995%.
2.6 helium-hydrogen mixed gas, helium 98～94%, hydrogen 2～6% mix, and purity is more than 99.995%.
2.5 copper powder, glass wool, platinum carbon, EA 6000 reductive agents.
3 test methods
3.1 measure carbon, hydrogen, nitrogen, sulphur instrumental correction
Instrument blank assay: do not open oxygen valve, do not add sample, measure blank to the instrument requirement state; Open oxygen valve, carry out blank assay to instrument requirement state continuously.Use cystine standard substance (carbon content 29.99%, hydrogen richness 5.03%, nitrogen content 11.67%, sulfur content 26.69%) to carry out instrumental correction; Accurately take by weighing and measure the K factor about cystine 1mg; Measure blank then, replication is to meeting instrument replicate determination requirement.The instrument condition of work is seen table 1.
Table 1 is measured carbon, hydrogen, nitrogen, sulphur condition of work
3.2 measure the oxygen instrumental correction
Instrument blank assay: do not open helium-hydrogen valve, do not add sample, measure blank to the instrument requirement state; Open helium-hydrogen valve, carry out blank assay to instrument requirement state continuously.Use benzoic acid standard substance (oxygen content 26.20%) to carry out instrumental correction.Accurately take by weighing and measure the K factor about benzoic acid 1mg, measure blank then, K factor replication is to meeting instrument replicate determination requirement.The instrument condition of work is seen table 2.
Table 2 is measured the oxygen condition of work
3.3 the instrumental correction K factor
The K factor calculation is undertaken by formula (1).
In the formula:
K---carbon, hydrogen, oxygen, nitrogen, the sulphur K factor, unit is joule every milligram (J/mg);
P---carbon, hydrogen, oxygen, nitrogen, sulfur content in the standard model, unit is percentage composition (%);
H
0---the thermal conductance value of carbon, hydrogen, oxygen, nitrogen, sulphur in the cystine standard specimen, unit is joule (J);
Δ H
0---blank thermal conductance value, unit is joule (J);
M
0---the standard substance quality, unit is a milligram (mg).
3.4 measure
Accurately weighing oil sample 1.000mg (being accurate to 0.001mg) seals in sample cup, puts into automatic sampler, and Pintsch process, middle burning produce N
2, H
2O, CO
2, SO
2, separating, measure through chromatographic column, computing machine calculates carbon in the oil, hydrogen, oxygen, nitrogen, sulphur percentage composition automatically, and carbon, hydrogen, oxygen, nitrogen, sulfur content are calculated by formula (2) in the oil sample.
In the formula:
X---oxygen, carbon, hydrogen, nitrogen, sulfur content in the oil, unit is a percentage composition, %;
H---the thermal conductance value of oxygen, carbon, hydrogen, nitrogen, sulphur in the oil, unit is joule (J);
Δ H---blank thermal conductance value, unit is joule (J);
M---oil sample mass, unit are milligram (mg);
K---oxygen, carbon, hydrogen, nitrogen, the sulphur K factor, unit is joule every milligram (J/mg).
2 position effective digitals behind the result of calculation reservation radix point.
3.5 mensuration result
Through measuring, carbon, hydrogen, oxygen, nitrogen, sulphur percentage composition are seen table 3 in the oil (heavy oil).
Oxygen, carbon, hydrogen, nitrogen, sulphur are measured the result in table 3 oil
4 determination experiments
4.1 detection limit experiment
Blank 10 times of METHOD FOR CONTINUOUS DETERMINATION is measured carbon, hydrogen, nitrogen, sulphur and oxygen content respectively, and basis of calculation deviation is seen table 4.
Table 4 measurement blank assay (n=10, %)
Calculating measurement standard deviation S, is the detection limit of determined element with 3 times of measurement standard deviation, calculates theoretical detection limit: carbon detection limit 0.02%, hydrogen detection limit 0.04%, nitrogen detection limit 0.04%, sulphur detection limit 0.04%, oxygen detection limit 0.03%.
Instrument carbon, hydrogen, nitrogen, sulphur, detecting of oxygen are limited to 0.001mg, convert to sample to be equivalent to 0.02～0.05%, and the experiment detection limit is consistent with the instrument detection limit, satisfies the mensuration demand.
4.2 stability experiment
METHOD FOR CONTINUOUS DETERMINATION cystine standard substance, benzoic acid standard substance, oil sample respectively 10 times, measurement stability is seen table 5.
The experiment of table 5 standard substance, oil sample measurement stability (n=10, %)
Measure relative standard deviation (RSD): carbon 0.45～0.65%, hydrogen 1.44～2.05%, nitrogen 1.45～2.76%, sulphur 1.21～2.41%, oxygen 1.02～3.25%.Nitrogen, oxygen content are all less than 1% in the oil, and it is slightly poor to measure repeatability, but measure relative standard deviation RSD all less than 3.5%, the apparatus measures good stability, and it is accurate to measure the result, satisfies the detection needs.
4.2 mensuration repeated experiment
4.2.1 carbon, hydrogen, nitrogen, the experiment of sulphur recovery of standard addition
After quantitatively taking by weighing oil sample, accurately add the cystine standard substance, be equivalent to quantitatively add carbon, hydrogen, nitrogen, sulphur, carry out the recovery of standard addition experiment, the result sees table 6～table 9.
Carbon mark-on recovery experiment in table 6 oil (n=10, mg)
Hydrogen mark-on recovery experiment in table 7 oil (n=10, mg)
Nitrogen mark-on recovery experiment in table 8 oil (n=10, mg)
Sulphur mark-on recovery experiment in table 9 oil (n=10, mg)
Carbon, hydrogen, nitrogen, sulphur recovery of standard addition experimental result in the oil: carbon 90.1～112.8%, hydrogen 92.0～108.0%, nitrogen 94.0～116.9%, sulphur 87.1～105.3%, it is accurate to measure the result.
4.2.2 measure the experiment of oxygen recovery of standard addition
After quantitatively accurately taking by weighing oil sample, add the benzoic acid standard substance, be equivalent to quantitatively add oxygen, carry out the recovery of standard addition experiment, the result sees table 10.
Oxygen mark-on recovery experiment in table 10 oil (n=10, mg)
Oxygen recovery of standard addition 87.3～106.8% in the oil, it is accurate to measure the result.
Claims (5)
1. the assay method of carbon, hydrogen, oxygen, nitrogen, sulphur in the oil is characterized in that being made up of following steps:
One, accurate weighing oil sample places special aluminium quality sample cup, sealing;
Two, per 1 milligram of oil sample quantitatively feeds carrier gas (helium 0.14MPa), power gas (argon gas 0.4MPa), burning gas (oxygen 0.1MPa), measures carbon, hydrogen, nitrogen, sulphur;
Per 1 milligram of oil sample quantitatively feeds carrier gas (helium-hydrogen mixed gas 0.14MPa), power gas (argon gas 0.4MPa), measures oxygen;
Three, oil is through Pintsch process, burn in pure oxygen, and the carbon in the sample, hydrogen, nitrogen, sulphur change into gas CO
2, H
2O, N
2, SO
2Oil is through Pintsch process, burn in helium-hydrogen mixed gas, and the oxygen in the sample changes into gas CO;
Four, CO
2, H
2O, CO, N
2, SO
2Separate through chromatographic column, thermal conductance detects carbon, hydrogen, oxygen, nitrogen, sulphur percentage composition.
Elemental analyser is proofreaied and correct with the standard substance cystine, measures carbon, hydrogen, nitrogen, sulfur content in the oil; Proofread and correct with the standard substance benzoic acid, measure oxygen content in the oil.
2. the assay method of carbon, hydrogen, oxygen, nitrogen, sulphur in the oil according to claim 1, it is characterized in that described oil is a large amount of animals and plants death before and after the Paleozoic Era and secondary era after, its organic substance constantly decomposes, deposit formation gradually.Oil is organic mixture, mainly contains alkane, naphthenic hydrocarbon, aromatic hydrocarbon.
3. the assay method of carbon, hydrogen, oxygen, nitrogen, sulphur in the oil according to claim 1, the helium of use, helium-hydrogen mixed gas, argon gas, oxygen are high-purity gas, and purity is more than 99.995%.Measure carbon, hydrogen, nitrogen, sulphur calibration instrument carbon content 29.99%, hydrogen richness 5.03%, nitrogen content 11.67%, sulfur content 26.69% with the standard substance cystine; Measure carbon, hydrogen, nitrogen, sulphur calibration instrument with standard substance benzoic acid oxygen content 26.20%, carbon content 68.85%, hydrogen richness 4.95% (be used to measure the oxygen content instrumental correction, only use the content of oxygen).
4. the assay method of carbon, hydrogen, oxygen, nitrogen, sulphur in the oil according to claim 1; It is characterized in that being applicable to carbon in the oil, hydrogen, oxygen, nitrogen, sulfur content all greater than 0.01% detection, detection limit: carbon 0.02%, hydrogen 0.04%, oxygen 0.03%, nitrogen 0.04%, sulphur 0.04%.
5. the assay method of carbon, hydrogen, oxygen, nitrogen, sulphur in the oil according to claim 1; It is characterized in that being applicable to carbon in the oil, hydrogen, oxygen, nitrogen, sulfur content all greater than 0.01% detection, recovery of standard addition: carbon 90.1～112.8%, hydrogen 92.0～108.0%; Oxygen 87.3～106.8%; Nitrogen 94.0～116.9%, sulphur 87.1～105.3%, carbon, hydrogen, oxygen, nitrogen, sulphur recovery of standard addition scope 87.1～116.9%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105424866A (en) * | 2015-12-01 | 2016-03-23 | 天津师范大学 | Method for quickly analyzing gas mixture by determining hydrogen and carbon monoxide |
| CN106841486A (en) * | 2016-12-20 | 2017-06-13 | 南华大学 | The qualitative and quantitative analysis method of elementary sulfur in a kind of liquefied petroleum gas |
| CN111965282A (en) * | 2020-08-18 | 2020-11-20 | 中国地质科学院矿产资源研究所 | Ultra-micro sulfur isotope analysis system and analysis method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783741A (en) * | 1997-01-31 | 1998-07-21 | Atlantic Richfield Company | Capillary furnace for improved peak resolution in gas isotope chromatography |
| CN101915812A (en) * | 2010-07-20 | 2010-12-15 | 云南出入境检验检疫局检验检疫技术中心 | Method for measuring carbon, hydrogen, nitrogen and sulfur in lavender |
| CN102053126A (en) * | 2010-11-04 | 2011-05-11 | 云南出入境检验检疫局检验检疫技术中心 | Method for measuring nitrogen, hydrogen, carbon and sulfur in tree moss concrete |
-
2011
- 2011-09-07 CN CN201110262507A patent/CN102323296A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783741A (en) * | 1997-01-31 | 1998-07-21 | Atlantic Richfield Company | Capillary furnace for improved peak resolution in gas isotope chromatography |
| CN101915812A (en) * | 2010-07-20 | 2010-12-15 | 云南出入境检验检疫局检验检疫技术中心 | Method for measuring carbon, hydrogen, nitrogen and sulfur in lavender |
| CN102053126A (en) * | 2010-11-04 | 2011-05-11 | 云南出入境检验检疫局检验检疫技术中心 | Method for measuring nitrogen, hydrogen, carbon and sulfur in tree moss concrete |
Non-Patent Citations (1)
| Title |
|---|
| 南爱玲 等: "元素分析仪法测定石油产品中氧含量的影响因素初探", 《现代科学仪器》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105424866A (en) * | 2015-12-01 | 2016-03-23 | 天津师范大学 | Method for quickly analyzing gas mixture by determining hydrogen and carbon monoxide |
| CN106841486A (en) * | 2016-12-20 | 2017-06-13 | 南华大学 | The qualitative and quantitative analysis method of elementary sulfur in a kind of liquefied petroleum gas |
| CN111965282A (en) * | 2020-08-18 | 2020-11-20 | 中国地质科学院矿产资源研究所 | Ultra-micro sulfur isotope analysis system and analysis method |
| CN111965282B (en) * | 2020-08-18 | 2023-08-29 | 中国地质科学院矿产资源研究所 | Ultra-trace sulfur isotope analysis system and analysis method |
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Application publication date: 20120118 |